Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Completely biodegradable composites of poly(propylene carbonate) and short,lignocellulose fiber Hildegardia populifolia

The composites of biodegradable poly(propylene carbonate) (PPC) reinforced with short Hildegardia populifolia natural fiber were prepared by melt mixing followed by compression molding. The mechanical properties, thermal properties, and morphologies of the composites were studied via static and dynamic mechanical measurements, thermogravimetric analysis, and scanning electron microscopy (SEM) techniques, respectively. Static tensile tests showed that the stiffness and tensile strength of the composites increased with an increasing fiber content. However, the elongation at break and the energy to break decreased dramatically with the addition of short fiber. The relationship between the experimental results and the compatibility or interaction between the PPC matrix and fiber was correlated. SEM observations indicated good interfacial contact between the short fiber and PPC matrix. Thermogravimetric analysis revealed that the introduction of short Hildegardia populifolia fiber led to a slightly improved thermooxidative stability of PPC. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 666–675, 2004     

Studies of photooxidative degradation of poly(vinyl chloride)/poly(ethylene oxide) blends

The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 2004     

New liquid‐crystalline poly(ester amide)s: The role of nitro groups in the phase behavior

New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004     

The effect of compatibilization and rheological properties of polystyrene and poly(dimethylsiloxane) on phase structure of polystyrene/poly(dimethylsiloxane) blends

The compatibilization effect of polystyrene (PS)‐poly(dimethylsiloxane) (PDMS) diblock copolymer (PS‐b‐PDMS) and the effect of rheological properties of PS and PDMS on phase structure of PS/PDMS blends were investigated using a selective extraction technique and scanning electron microscopy (SEM). The dual‐phase continuity of PS/PDMS blends takes place in a wide composition range. The formation and the onset of a cocontinuous phase structure largely depend on blend composition, viscosity ratio of the constituent components, and addition of diblock copolymers. The width of the concentration region of the cocontinuous structure is narrowed with increasing the viscosity ratio of the blends and in the presence of the small amount diblock copolymers. Quiescent annealing shifts the onset values of continuity. The experimental results are compared with the volume fraction of phase inversion calculated with various theoretical models, but none of the models can account quantitatively for the observed data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 898–913, 2004     

Viscoelastic behavior of polypropylene/nitrile rubber thermoplastic elastomer blends: Application of Kerner's models for reactively compatibilized and dynamically vulcanized systems

The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X‐ray diffraction

The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 2004     

Physical properties of glycosaminoglycan hydrogels

The chemical composition of glycosaminoglycan (GAG) hydrogels was found to have a profound effect on the physical properties of gels. Hyaluronan (HA) and chondroitin sulfate (CS) were each modified with adipic dihydrazide (ADH) with carbodiimide chemistry. The resulting polymer was crosslinked with various concentrations of poly(ethylene glycol) dialdehyde (PEG‐diald) to produce a series of hydrogels. The physical properties of these GAG hydrogels varied in a concentration‐dependent fashion. Maximal crosslinking was observed at a theoretical crosslinking of 50% for the HA‐ADH‐PEG‐diald hydrogels and 75% for the CS‐ADH‐PEG‐diald hydrogels. Adding PEG‐diald beyond the optimum for crosslinking prolonged the in vitro enzymatic degradation time of the hydrogels. The swelling of the crosslinked GAG hydrogels was correlated with the amount of PEG‐diald used rather than with the crosslinking density. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4344–4356, 2004     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004