Phase equilibria of quasi-ternary systems consisting of multicomponent polymers 1 and 2 in a single solvent. II. Cloud point curve

Theoretical equations and a calculation method giving cloud point curve (CPC) for a multicomponent polymer 1/multicomponent polymer 2/single solvent system (i.e. quasi-ternary system) were derived on the basis of the Flory-Huggins solution theory. The systematic calculations based on this method were carried out to examine the effects on CPC of the type of molecular weight distribution, the polydispersity and the weight-average degree of polymerisation of the two original polymers, and three thermodynamic interaction parameters between solvent-polymer 1 (X₀₁), solvent-polymer 2 (X₀₂) and polymer 1-polymer 2 (X₁₂). The shape of CPC sensitively depends on the polydispersity of the original polymer and, with an increase in polydispersity, the immiscibility region becomes wider.     

Temperature responsive bio-compatible polymers based on poly(ethylene oxide) and poly(2-oxazoline)s

This review covers the LCST behavior of two important polymer classes in aqueous solution, namely poly(2-oxazoline)s and systems whose thermo-responsiveness is based on their structural similarity to poly(ethylene oxide) (PEO). In order to elucidate the progress that has been made in the design of new thermo-responsive copolymers, experimental data that were obtained by different research groups are compared in detail. Copolymerization with hydrophilic or hydrophobic comonomers represents a suitable method to tune the coil to globule transition temperature of several homopolymers, and incorporation of other monomers provided further interesting features, such as pH responsiveness or sensing properties. In addition, living and controlled polymerization techniques enabled access to defined end groups and more advanced polymer architectures, such as graft copolymers or double responsive block copolymers. The effect of such structural variations on the temperature responsive behavior of the (co)polymers is discussed in detail.     

Miscibility in blends of linear and branched poly(ethylene oxide) with methacrylate derivative random copolymers and estimation of segmental χ parameters

Miscibility in the blends of poly(ethylene oxide) (PEO) with n-hexyl methacrylate-methyl methacrylate random copolymers (HMA-MMA) and 2-ethylhexyl methacrylate-MMA random copolymers (EHMA-MMA) was evaluated using glass transition and light scattering methods. EHMA-MMA was more miscible with PEO than HMA-MMA. Both blends of PEO with HMA-MMA and EHMA-MMA showed UCST-type miscibility although homopolymer blends PEO/PMMA were predicted to be of LCST-type. This was attributed to an increase in the exchange enthalpy with increasing HMA or EHMA composition in the random copolymer. From the copolymer composition dependence of miscibility the segmental χ parameters of HMA/MMA, EHMA/MMA, EO/HMA and EO/EHMA were estimated using the Flory-Huggins theory extended to random copolymer systems. Miscibility in the blends of branched PEO with HMA-MMA whose HMA copolymer composition was 0.16 was compared with that in the linear PEO blends. The former blends were more miscible with HMA-MMA than the latter one by about 35 °C at the maximum cloud point temperature.     

The study of poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyrene)/poly(ethylene oxide) blends

Different hydroxyl content poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyene) [PS(OH)‐X] copolymers were synthesized and blends with 2,2,6,6‐tetramrthyl‐piperdine‐1‐oxyl end spin‐labeled PEO [SLPEO] were prepared. The miscibility behavior of all the blends was predicted by comparing the critical miscible polymer–polymer interaction parameter (χ_crit) with the polymer–polymer interaction parameter (χ). The micro heterogeneity, chain motion, and hydrogen bonding interaction of the blends were investigated by the ESR spin label method. Two spectral components with different rates of motion were observed in the ESR composite spectra of all the blends, indicating the existence of microheterogeneity at the molecular level. According to the variations of ESR spectral parameters T_a, T_d, ΔT, T_50G and τ_c, with the increasing hydroxyl content in blends, it was shown that the extent of miscibility was progressively enhanced due to the controllable hydrogen bonding interaction between the hydroxyl in PS(OH) and the ether oxygen in PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2312–2317, 2004     

Fractional Crystallization and Phase Segregation in Binary Miscible Poly(butylene succinate)/Poly(ethylene oxide) Crystalline Blends: Effect of Crystallization Temperature

The effects of crystallization temperature of PBS (T_IC,PBS) on the fractional crystallization, phase segregation, and crystalline morphology of PEO in their miscible crystalline/crystalline blends are investigated. The crystallization kinetics and phase segregation of PEO are considerably influenced by T_IC,PBS. A higher T_IC,PBS results in the crystallization of PEO at an extremely large degree of supercooling and may facilitate the segregation of PEO within the interlamellar regions of PBS. At a high T_IC,PBS (e.g., 95 °C), the long period, thickness of amorphous and crystalline layers of PBS increase upon blending with PEO. The T_IC,PBS dependence of phase segregation of the PEO component is discussed from a thermodynamic as well as a kinetic perspective.

     

Miscibility of oligomeric poly(dimethyl siloxanes) with long-chain unbranched alkanes: 2. Unsymmetrical cloud point curves

Previously obtained cloud point curves for mixtures of oligomeric poly(dimethyl siloxanes) (weight fraction W₁) with oligomeric polyethylenes have been supplemented by the use of samples of higher molecular weight. Initial flat regions at low-medium W₁ as well as a slight shoulder at extremely high W₁ are now considered to be due to crystallization, since the temperatures at which they occur are the melting points of the oligoethylenes. The actual cloud point curves were of an unsymmetrical dome shape, the form of which could not be simulated by using a concentration-independent interaction parameter g in the Flory-Huggins equation. However, spinodals calculated by assuming a quadratic dependence of g on composition were of the same shape as the experimental cloud point curves. The critical compositions calculated on this basis were also close to the experimental ones.     

Blends containing amphiphilic polymers IV. Poly(N‐1‐alkyl itaconamic acids) with poly(2‐vinylpyridine) and poly(4‐vinylphenol)

The phase behavior of blends containing Poly(N‐1‐alkyl itaconamic acids) (PNAIA) with Poly(2‐vinylpyrindine) (P2VPy) and Poly(4‐vinylphenol) (P4VPh) were analyzed by Diferential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR). Miscibility over the whole range of compositions is observed in both systems. All the blends show thermograms exhibiting distinct single glass transition temperatures (T_g), which are intermediate to those of the pure components. The Calorimetric Analysis using Gordon Taylor, Couchman, and Kwei treatments allows conclusion that interactions between the components is favorable to the miscibility. FTIR analysis of the blends suggests that the driving force for miscibility is hydrogen bonding formation. The variation of the absorptions of the carbonyl groups of PNAIA and the hydroxyl groups of P4VPh allows one to attribute the miscibility to weak acid base like interactions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1245–1250, 2002; DOI 10.1002/app.10453     

Morphology,dynamic mechanical,and electrical properties of bio‐based poly(trimethylene terephthalate) blends,part 1: Poly(trimethylene terephthalate)/poly(ether esteramide)/polyethylene glycol 400 bis(2‐ethylhexanoate) blends

Bio‐based PTT and PTT blends with PEEA of two different ion contents (275 ppm Na and 3515 ppm Na) and PEG 400 bis (2‐ethylhexanoate) were prepared by melt processing. The blends were characterized by differential scanning calorimetry, dynamic mechanical analysis, transmission electron microscopy, and atomic force microscopy. Electro‐static performance was also investigated for those PTT blends since PEEA is known as an ion conductive polymer. Here we confirmed that PEG 400 bis (2‐ethylhexanoate) improves the static decay performance of PTT/PEEA blends. DMA strongly suggests that PEG 400 bis (2‐ethylhexanoate) and PEEA are miscible pairs, and PEG 400 bis (2‐ethylhexanoate) selectively goes into the PEEA phase rather than the PTT phase, which lowers the T_g of PEEA. Besides topographic analysis of morphology and phase separation, tunneling atomic force microscopy was also applied to see if we can observe the surface directly for the static dissipative material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011