Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide)

Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to ¹H and ¹³C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226     

Cracking in polylactide spherulites

A polylactide of high optical purity was crystallized between 100 and 140 °C, in‐between two glass slides, and its morphology was investigated by polarizing optical microscopy, scanning electron microscopy, and atomic force microscopy, during subsequent heating and cooling cycles between ?15 °C and the crystallization temperature. It was found that dark circular rings show up on cooling on top of the spherulites and represent cracks of about 300 nm in width. This phenomenon is completely reversible, and the heating–cooling curves are centered at about 56 °C, which coincide with the T_g of polylactide. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3308–3315, 2005     

Conformational behavior of poly(L-lactide) studied by infrared spectroscopy

This paper reports the analysis of the C=O stretching region of poly(L-lactide). This spectral band splits into up to four components, a phenomenon that a priori can be explained in terms of carbonyl-carbonyl coupling or specific interactions (such as C-H...O hydrogen bonding or dipole-dipole). Hydrogen bonding can be discarded from the analysis of the C-H stretching spectral region. In addition, low molecular weight dicarbonyl compounds of chemical structure similar to that of PLLA, such as diacyl peroxides, show a remarkable splitting of the carbonyl band attributed to intramolecular carbonyl-carbonyl coupling. Several mechanisms can be responsible for this behavior, such as mechanical coupling, electronic effects, or through-space intramolecular TDC (transition dipole coupling) interactions. Intermolecular dipole-dipole interactions (possible in the form of interchain TDC interactions) are proven to be of minor relevance taking into account the spatial structure of the PLLA conformers. The Simply Coupled Oscilator (SCO) model, which only accounts for mechanical coupling, has been found to predict adequately the relative intensity of the symmetric and asymmetric bands of dicarbonyl compounds. The dispersion curves predicted for PLLA by the SCO model also match those given by more general treatments, such as Miyazawa's first-order perturbation theory. Hence, the SCO model is adopted here as an adequate yet simple tool for the interpretation of band splitting caused by intramolecular coupling of polylactide. The four components observed in the C=O stretching band of semicrystalline PLLA are attributed to the four possible conformers: gt, gg, tt, and tg. The narrow bands observed for the interlamellar material are attributed to highly ordered chains, indicating the absence of a truly amorphous phase in the crystalline polymer. The interphase seems to extend over the whole interlamellar region, showing the features of a semiordered metastable phase. In amorphous PLLA, bands corresponding to gt, gg, and tt conformers also can be resolved by second derivative techniques, and curve-fitting results provide information about the conformational population at different temperatures.     

Crystallinity and Crystalline Confinement of the Amorphous Phase in Polylactides

Summary: Stereorregular polylactides such as poly (L-lactide) (PLLA) or poly (D-lactide) result from polymerization of optically pure lactides and are semicrystalline. Optically non-active poly(D,L-lactide) (PDLLA) can be regarded as random or atactic copolymers, show a random moiety distribution, and are completely amorphous. In this work three phases, comprising mobile amorphous fraction (MAF, χ_MA), rigid amorphous fraction (RAF, χ_RA) and crystalline fraction (χ_c) were determined in PLLA. It will be shown that RAP fraction not only elevates Tg but also increases the dynamic fragility (m) of polylactide chains around the Tg. These results agree with reported cases in which topologycal constraints inhibit longer range dynamics and suggest a smaller length scale of cooperativity of chains in confined environments.     

Utilization of heavy-atom effect quenching of pyrene fluorescence to determine the intramembrane distribution of halothane

The interaction of halothane (CF₃CHBrCl) with dipalmitoylphosphatidylcholine (DPPC) membranes containing varying amounts of dipalmitoylphosphatidylglycerol (DPPG) was examined via heavy atom effect quenching of pyrene fluorescence by halothane. The effect of halothane on pyrene fluorescence is consistent with a kinetic model based upon the assumption of the existence of two populations of pyrene in the membrane: one accessible to interactions with halothane; the second inaccessible to halothane on the time scale of the pyrene fluorescence excited state. Both populations of pyrene are affected by the presence of halothane in the membrane. The rate of halothane quenching of pyrene fluorescence is increased significantly for all DPPG/DPPC membranes compared to pure DPPC membranes indicating that any DPPG in the membrane facilitates interaction between halothane and pyrene even though the measured partition coefficients indicate that little change in total halothane concentration in the membrane as a whole occurs as a function of percent DPPG in DPPG/DPPC mixtures.
It is speculated that phase boundaries play an important role in determining the behavior of this model system by determining the location of the pyrene probe. The heavy atom effect quenching of pyrene by halothane provides a useful probe of phase boundaries in membranes.     

Phase behavior and effects of microstructure on viscoelastic properties of a series of polylactides and polylactide/poly(ε-caprolactone) copolymers

Dynamic viscoelastic measurements were combined with differential scanning calorimetry (DSC) and atomic force microscopy (AFM) analysis to investigate the rheology, phase structure, and morphology of poly(l-lactide) (PLLA), poly(ε-caprolactone) (PCL), poly(d,l-lactide) (PDLLA) with molar composition l-LA/d-LA?=?53:47, and poly(l-lactide-co-ε-caprolactone) (PLAcoCL) with molar composition l-LA/CL?=?67:33. After melt conformation, both copolymers PDLLA and PLAcoCL were found to be amorphous whereas PLLA and PCL presented partial crystallinity. The copolymers and PCL were considered as thermorheologically simple according to the rheological methods employed. Therefore, data from different temperatures could be overlapped by a simple horizontal shift (a _T) on elastic modulus, G′, and loss modulus, G′, versus frequency graph, generating the corresponding master curves. Moreover, these master curves showed a dependency of G″≈ω and G′≈ω ² at low frequencies, which is a characteristic of homogeneous melts. For the first time, fundamental viscoelastic parameters, such as entanglement modulus G _N ⁰ and reptation time τ _d, of a PLAcoCL copolymer were obtained and correlated to chain microstructure. PLLA, by contrast, was unexpectedly revealed as a thermorheologically complex liquid according to the failure observed in the superposition of the phase angle (δ) versus the complex modulus (G*); this result suggests that the narrow window for rheological measurements, chosen to be close to the melting point centered at 180 °C thus avoiding thermal degradation, was not sufficient to assure an homogeneous behavior of PLLA melts. The understanding of the melt rheology related to the chain microstructural aspects will help in the understanding of the complex phase structures present in medical devices.     

Polymerized ionic liquid functionalized multi-walled carbon nanotubes/polyetherimide composites

Thin polyetherimide (PEI) films containing 0.1–3 wt.% multi-walled carbon nanotubes (MWCNTs), have been prepared from three types of MWCNTs, namely pristine, oxidized and polymerized ionic liquid (PIL) functionalized CNTs. Oxidized and PIL functionalized CNTs (CNT–PIL) showed better dispersion in the matrix compared to pristine CNTs. For CNT–PIL, alignment of CNTs has been observed in the matrix. Regardless of the type of CNTs, their incorporation led to an increased thermal stability of the polymer matrix. Dynamic mechanical analysis showed that storage modulus increased by up to 25% (3 wt.% CNT–PIL) and an increase in the height of the damping peaks (tan δ). The addition of CNTs did not have any significant influence on the tensile properties and T_g of the polymer, and the electrical conductivity did not decrease in the case of modified CNTs.     

Exothermal Process in Miscible Polylactide/Poly(vinyl phenol) Blends: Mixing Enthalpy or Chemical Reaction?

Summary: In a previous paper (Macromolecules, 2005 , 38, 9221), the enthalpy of mixing in poly(DL ‐lactide) /poly(vinyl phenol) blends was directly measured by DSC. The first DSC scan for solution/precipitation blends showed phase separation, but miscibility was observed in the second DSC scan. Hence, miscibility was achieved after thermal treatment, an unusual behavior in polymer blend current research. However, the exothermal event observed during the first heating scan could also be the result of a chemical reaction. In this work, a new research study conducted to elucidate the nature of the exothermal heat observed in PDLA/PVPh during the first DSC heating scan. Since the single‐phase PDLLA/PVPh blend obtained after thermal treatment can be redissolved and reprecipitated, results obtained in the consecutive DSC scan prove that the process is completely reversible. Furthermore, GPC and ¹³C NMR results provide evidence that there is no change in the chemical structure of the studied polymers before and after the thermal treatment, which evidences the absence of transesterification reactions. Therefore, it can be concluded that the exothermal heat is the result of a mixing process, and miscibility is a consequence of specific interactions.

New structure expected for transesterfication reactions.