Poly(ethylene glycol-co-propylene glycol) as a Macromolecular Plasticizing Agent for Polylactide: Thermomechanical Properties and Aging

Finding a Suitable plasticizer for polylactide (PLA) is necessary to overcome its brittleness and enlarge its range of applications. In this study, commercial PLA was melt-blended with a new plasticizer, an ethylene glycol/propylene glycol random copolymer [poly(ethylene glycol-co-propylene glycol) (PEPG)] with a typical number-average molecular weight of 1.2 kDa and an ethylene glycol content of 78.7 mol %. The thermal properties, crystallization behavior, and mechanical properties of the quenched blends and the properties of the blends after storage for 2 months under the ambient conditions were investigated in detail. The advantage of using PEPG is that it does not crystallize at room temperature and has good compatibility with PLA. The quenched PLA/PEPG blends were homogeneous and amorphous systems. With an increase in the PEPG content (5-20%), the glass-transition temperature, tensile strength, and modulus of the blends decreased, whereas the elongation at break and crystallizability increased dramatically. The cold crystallization of PLA resulted in phase separation of the PLA/PEPG blends by annealing of the blends at the crystallization temperature.

Crystallization Behavior and Mechanical Properties of Crosslinked Plasticized Poly(L-lactic acid)

Enhancing the stability of plasticized poly(L-lactic acid) (PLLA) with poly (ethylene glycol) (PEG) is necessary for its practical application. In this study, plasticized PLLA (PLLA/PEG 80/20 wt/wt) was crosslinked under I-ray (Co-60) in the presence of triallyl isocyanurate (TALC) as crosslinking agent. FTIR analysis revealed that PLLA, PEG, and TALC formed a cocrosslinking structure. Crystallization behavior and mechanical properties of the crosslinked plasticized PLLA were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests. Experimental results indicated that the crystallization behaviors of both PEG and PLLA in the blends were restrained after irradiation. The melting peak of PEG in the crystallized samples disappeared at a low irradiation doses about 10 kGy. Although PLLA still owned the behavior of crystallize, its cold crystallization temperature and glass transition temperature shifted to higher temperature. Mechanical properties of the plasticized PLLA were strengthened through crosslinking. Both yield strength and elastic modulus of the samples increased after crosslinking.

Solvent-induced Morphology of the Binary Mixture of Diblock Copolymer in Thin Film: The Block Length and Composition Dependence of Morphology

A series of binary SB blend samples with various overall volume fraction of PS (Phi(PS)) and different discrete distribution of the block length (denoted as d(PS) or d(PB)) were prepared by mixing various asymmetric poly(styrene)-block-poly(butadiene) (SB) block copolymers with a symmetric SB block copolymer. The influences of the external solvent field, composition, and the block length distribution on the morphologies of the blends in the thin films were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The experimental results revealed that after solvent annealing, the interface of the blend thin films depended mainly on the cooperative effects of the annealing solvent and the inherently interfacial curvature of the blends. Upon exposure to the saturated vapor of cyclohexane, which has preferential affinity for the PB block, a "threshold" of Phi(PS) (approximate 0.635-0.707) was found. Below such threshold, the influence of the annealing solvent played an important role on the interfacial curvature of the blend thin film.

Effect of peroxide crosslinking on thermal and mechanical properties of poly(epsilon-caprolactone)

Poly(epsilon-caprolactone) (PCL), a saturated polyester, derived from ring-opening polymerization of epsilon-caprolactone, was chemically crosslinked with various amounts of benzoyl peroxide (BPO) by a two-step method by first evenly dispersing the BPO into the PCL matrix and then crosslinking at elevated temperature. The gel fraction increased with an increase in BPO content. The modified Charlesby-Pinner equation was used to calculate the ratio of chain scission and crosslinking. The results showed that both scission and crosslinking occurred, and that crosslinking predominated over scission. The number-average molecular weight between the crosslinks determined by the rubber elasticity theory using the hot set test showed a decrease with increasing BPO content. The melting temperature and crystallinity decreased with an increase in BPO content, and the crystallization temperature increased after crosslinking. Dynamic mechanical analysis results showed a decrease in the glass transition temperature as a result of chemical crosslinking of PCL. This was explained by the observed reduction in crystallinity and the increase in free volume due to restrictions in chain packing.

Thermal and mechanical properties of poly(epsilon-caprolactone) crosslinked with gamma radiation in the presence of triallyl isocyanurate

Poly(epsilon-caprolactone) was crosslinked by gamma radiation in the presence of triallyl isocyanurate. The influence of gamma-radiation crosslinking on the thermal and mechanical properties of poly(epsilon-caprolactone)/triallyl isocyanurate was investigated. Differential scanning calorimetry analyses showed differences between the first and second scans. Dynamic mechanical analysis showed an increase in the glass-transition temperature as a result of the radiation crosslinking of poly(epsilon-caprolactone). Thermogravimetric analysis showed that gamma-radiation crosslinking slightly improved the thermal stability of poly(epsilon-caprolactone). The 7 radiation also strongly influenced the mechanical properties. At room temperature, crosslinking by radiation did not have a significant influence on the Young's modulus and yield stress of poly(E-caprolactone). However, the tensile strength at break and the elongation at break generally decreased with an increase in the crosslinking level. When the temperature was increased above the melting point, the tensile strength at break, elongation at break, and Young's modulus of poly(epsilon-caprolactone) were also reduced with an increase in the crosslinking level. The yield stress disappeared as a result of the disappearance of the crystallites.

Evolution of phase morphology of high impact polypropylene particles upon thermal treatment

Solvent fractionation and differential scanning calorimetry (DSC) results show that high impact polypropylene (hiPP) produced by a multistage polymerization process consists of PP homopolymer, amorphous ethylene-propylene random copolymer (EPR), and semicrystalline ethylene-propylene copolymer. For the original hiPP particles obtained right after polymerization, direct transmission electron microscopy (TEM) observation reveals a fairly homogeneous morphology of the ethylene-propylene copolymer (EP) phase regions inside, while the polyethylene-rich interfacial layer observed between the EP region and the iPP matrix supports that EP copolymers form on the subglobule surface of the original iPP particles. Compared with that in original hiPP particles, the dispersed EP domains in pellets have much smaller average size and relatively uniform size distribution, indicating homogenization of the EP domains in the hiPP by melt-compounding. Upon heat-treatment, phase reorganization occurs in hiPP, and the dispersed EP domains can form a multiple-layered core-shell structure, comprising a polyethylene-rich core, an EPR intermediate layer and an outer shell formed by EP block copolymer, which accounts to some extent for the good toughness-rigidity balance of the material.

Pressure effects on thermodynamics of phase behavior in polystyrene/methylcyclohexane solutions

The calculations presented in this paper are based on the Sanchez-Lacombe (SL) lattice fluid theory. The interaction energy parameter, g*(12)/k, required in this approach was obtained by fitting the cloud points of polystyrene (PS) /methyleyclohexane (MCH) polymer solutions under pressure. The SL lattice fluid theory was used to calculate the spinodals, the binodals, and the Flory-Huggins (FH) interaction parameter of the solutions. The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well. However, the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions. Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.

Syndiotactic 1,2-polybutadiene fibers produced by electrospinning

Syndiotactic 1,2-polybutadiene (s-PB) is a typical thermoplastic elastomer with various applications because of its high reactivity. In the past, it is difficult to form s-PB fibers with a diameter below 10 mu m because of the limitation of the conventional method such as melt spinning. Here, we report for the first time on the production of s-PB nanofibers by using a simple electrospinning method. Ultrafine s-PB fibers without beads were electrospun from s-PB solutions in dichloromethane and characterized by environmental scanning electron microscope (ESEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). At 4 wt.% concentration of s-PB, the average diameter of s-PB was about 130 nm. We found that dichloromethane was a unique suitable solvent for the electrospinning of s-PB fibers, and the structure of syndiotactic was changed through the electrospinning process.

Crystallization behavior of poly(epsilon-caprolactone) in poly(epsilon-caprolactone) and poly(vinyl methyl ether) mixtures

The morphological development and crystallization behavior of poly(epsilon-caprolactone) (PCL) in miscible mixtures of PCL and poly(vinyl methyl ether) (PVME) were investigated by optical microscopy as a function of the mixture composition and crystallization temperature. The results indicated that the degree of crystallinity of PCL was independent of the mixture composition upon melt crystallization because the glass-transition temperatures of the mixtures were much lower than the crystallization temperature of PCL. The radii of the PCL spherulites increased linearly with time at crystallization temperatures ranging from 42 to 49 degrees C. The isothermal growth rates of PCL spherulites decreased with the amount of the amorphous PVME components in the mixtures. Accounting for the miscibility of PCL/PVME mixtures, the radial growth rates of PCL spherulites were well described by a kinetic equation involving the Flory-Huggins interaction parameter and the free energy for the nuclei formation in such a way that the theoretical calculations were in good agreement with the experimental data. From the analysis of the equilibrium melting point depression, the interaction energy density of the PVME/PCL system was calculated to be -3.95 J/cm(3).

Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments.

Confined intra-molecular clustering in orientated polyethylene after annealing

Deuterated polyethylene tracer molecules with small amount of branches (12 C2H5- branches per 1000 backbone carbon atoms) were blended with a hydrogenated polyethylene matrix to form a homogenous mixture. The conformational evolution of the deuterated chains in a stretched semi-cry stall me film was observed via online small angle neutron scattering measurements during annealing at high temperatures close to the melting point. Because the sample was annealed at a temperature closely below its melting point, the crystalline lamellae were only partially molten and the system could not fully relax. The global chain dimensions were preserved during annealing. Recrystallization of released polymeric chain segments allows for local phase separation thus driving the deuterated chain segments into the confining interlamellar amorphous layers giving rise to an interesting intra-molecular clustering effect of the long deuterated chain. This clustering is deduced from characteristic small angle neutron scattering patterns. The confined phase separation has its origin in primarily the small amount of the branches on the deuterated polymers which impede the crystallization of the deuterated chain segments.

Suppression of phase separation in PC/PMMA blend film by thermoset oligomer

Phase separation of bisphenol A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) thin blend film is suppressed by addition of solid epoxy oligomer. Epoxy has strong intermolecular interactions with both PC and PMMA, while PC and PMMA are quite incompatible with each other. Consequently, phase separation in the PC/PMMA blend film pushes epoxy to the interface; at the same time, PC and epoxy react readily at the interface to form a cross-linking structure, binding PMMA chains together. Therefore, the interface between PC and PMMA is effectively reinforced, and the PC/PMMA thin blend film is stabilized against phase separation. On the other hand, only an optimal content of epoxy (i.e., 10 wt %) can serve as an efficient interfacial agent. In contrast to the traditional reactive compatibilization, here we observed that the cross-linking structure along the interface is much more stable than block or graft copolymers. Atomic force microscopy (AFM) is used to characterize the morphological changes of the blend films as a function of annealing time. Two-dimensional fast Fourier transform (2D-FFT) of AFM data allows quantitative investigation of the scaling behavior of phase separation kinetics.

Electrostatic interaction hybrids from water-borne conductive polyaniline and inorganic precursor containing carboxyl group

Electrostatic interaction conductive hybrids were prepared in water/ethanol solution by the sol-gel process from inorganic sol containing carboxyl group and water-borne conductive polyaniline (cPANI). The electrostatic interaction hybrids film displayed 1-2 orders of magnitude higher electrical conductivity in comparison with common hybrids film, showing remarkable conductivity stability against water soaking. Most strikingly, it displayed ideal electrochemical activity even in a solution with pH = 14, which enlarged the conducting polyaniline application window to strong alkaline media.

Water-resistant conducting hybrids from electrostatic interactions

Conductive hybrids were prepared in a water/ethanol solution via the Solgel process from an inorganic sol containing carboxyl groups and water-borne conductive polyaniline (cPANI). The inorganic sol was prepared by the hydrolysis and condensation of methyltriethoxysilane with the condensed product of maleic anhydride and aminopropyltriethoxysilane as a catalyst, for which the carboxyl counterion along the cPANI backbone acted as an electrostatic-interaction moiety. The existence of this electrostatic interaction could improve the compatibility of the two components and contribute to the homogeneous dispersion of cPANI in the silica phase. The electrostaticinteraction hybrids displayed a conductivity percolation threshold as low as 1.1 wt % polyaniline in an emeraldine base, showing 2 orders of magnitude higher electrical conductivity than that without electrostatic interactions. The electrostatic-interaction hybrids also showed good water resistance; the electrical conductivity with a cPANI loading of 16 wt % underwent a slight change after 14 days of soaking in water.