Infrared spectroscopic study on the crystallization of water in poly(vinyl methyl ether) aqueous solution during heating

The Fourier transform infrared (FTIR) results are consistent with the differential scanning calorimetric results and verify the anomalous crystallization of water in 50% poly(vinyl methyl ether) aqueous solution during heating. Below about ?34 °C, the water/polymer complex was not damaged, and the water still associated with the polymer. When heating to about ?34 °C, the associated water started to free from the unpolar (methyl group) and polar‐site (ether‐oxygen group) interaction fields of polymer gradually. Then crystallization of water was induced in this system at temperatures ranging from ?34 to ?24 °C. The FTIR data also indicate that the structure of water started to change first upon forming strong H bonds among water molecules, and then the dehydration of the polymer began to proceed subsequently when the anomalous crystallization of water occurred. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2772–2779, 2002     

Hydration changes of poly(2-(2-methoxyethoxy)ethyl methacrylate) during thermosensitive phase separation in water

Hydration changes of poly(2-(2-methoxyethoxy)ethyl methacrylate) (PMoEoEMa) during thermosensitive phase separation in water have been investigated by infrared spectroscopy. The C=O stretching band can be separated into three components assigned to non-hydrated carbonyl groups and singly and doubly hydrogen-bonded carbonyl groups (1728, 1709, and 1685 cm-1, respectively). Relatively large parts of the carbonyl groups (50% in 30 wt % solution) do not form hydrogen bonds even below the transition temperature (Tp) probably because they possess crowded positions near the backbone. The fraction of hydrogen-bonding carbonyl groups decreased during phase separation by approximately 0.2. Among five nu(C-H) bands, the highest- and the lowest-frequency bands (nu(C-H)A and nu(C-H)E) exhibited relatively large red shifts of 8 and 11 cm(-1), respectively. DFT calculations indicate that the formation of a H-bond between the ether oxygen and water leads to blue shifts of nu(C-H) of adjacent alkyl groups and has a larger effect than a direct H-bond to the alkyl groups, namely, C-H...O H-bonds. The fraction of hydrogen-bonding methoxy oxygens estimated from the position of the nu(C-H)A is 1 at Tp. This result indicates that the methoxy oxygens and the carbonyl are more favorably hydrated than the other at Tp, respectively.     

Molecular understanding of the UCST-type phase separation behavior of a stereocontrolled poly(N-isopropylacrylamide) in bis(2-methoxyethyl) ether

The upper critical solution temperature (UCST)-type phase separation of an isotactic-rich poly( N-isopropylacrylamide) (PNiPA) in bis(2-methoxyethyl) ether (diglyme) has been investigated by turbidity measurement and infrared (IR) spectroscopy. The IR spectra of stereocontrolled PNiPAs in various solvents have clearly indicated that the amide I bands do not directly reflect the tacticity of the polymer. The relative intensity of the amide I bands changes depending upon the molecular environment around the amide groups of PNiPA, which is influenced by the tacticity. During the UCST-type phase separation of the isotactic-rich PNiPA in diglyme, the amide I band at around 1625 cm (-1) changes. To link the IR spectral change with the molecular information, quantum chemical calculations have been carried out for NiPA n-mers ( n = 1-4) with an isotactic stereosequence. The result has suggested that the amide I band at around 1625 cm (-1) arises from a helical structure formed by the isotactic stereosequences in the PNiPA main chain with the aid of intramolecular CO...H-N hydrogen bonding. The experimental IR spectra have revealed that the helical structures are unfolded as the temperature rises. The folding and unfolding of the isotactic sequences in the main chain may induce the thermal change in the solubility of the isotactic rich PNiPA in diglyme, resulting in the UCST-type phase separation of the solution.     

Rheology and phase separation in polystyrene/poly(vinyl methyl ether) blends

Blends of monodisperse polystyrene and poly(vinyl-methyl-ether) of various compositions were prepared from solution in benzene. Dynamic rheological properties of these blends were studied at different temperatures below, near, and above T_s, the temperature of phase separation, and in a frequency range from 0.05 to 100 rad/s. A flattening in the storage modulus and an initial plateau for the complex viscosity were observed near and above T_s in the low-frequency region; in contrast, below T_s the behavior of the blends was similar to that of the homopolymers. The WLF superposition principle applies only at temperatures below T_s, i.e., in the miscible and homogeneous region. G″ versus G′ representations for the blends were found to be independent of temperature and to vary with composition in the miscible region but are temperature and composition-dependent in the immiscible region. It is also shown that the η″ versus η′ representation is a useful tool for characterizing phase separation of blends and is more sensitive than the classical frequency dependence of the material functions.     

Phase separation of poly(vinyl methyl ether) aqueous solution: a near-infrared spectroscopic study

The thermosensitive phase separation of poly(vinyl methyl ether) (PVME) aqueous solutions has been investigated using near-infrared spectroscopy in combination with two-dimensional correlation analysis, and a two-step phase separation mechanism during gradual heating has been established. Two-dimensional near-infrared (2D NIR) analysis results indicate that during this two-step process the dehydration of CH 2 groups occurs earlier than that of CH 3 groups. This result suggests that it is the change of the hydrophobic hydrocarbon chain conformation induced by heating that indirectly leads to the dehydration of the hydrophilic ether oxygen side groups.     

Characterization of phase separation of polystyrene/poly(vinyl methyl ether) blends using fluorescence

We have investigated the fluorescence emission spectra of pyrene and anthracene dyes covalently bonded to polystyrene (PS) upon phase separation from poly(vinyl methyl ether) (PVME). The specific chemical structure of the fluorescent labels is found to affect the measured phase separation temperature T_S, with fluorophores covalently attached in closer proximity to the PS backbone identifying phase separation a few degrees earlier. The sharp increase in fluorescence intensity upon phase separation that occurs for all fluorophores with little change in spectral shape is consistent with a mechanism of static fluorescence quenching resulting from the specific interaction with a nearby quenching molecular unit. Based on recent work that has identified a weak hydrogen bond occurring between the aromatic hydrogens of PS and the ether oxygen of PVME, we believe a similar weak hydrogen bond is likely occurring between the PVME oxygen and the aromatic dyes providing a local (few nanometer) sensitivity to phase separation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Evolution of concentration fluctuation during phase separation of polystyrene/poly(vinyl methyl ether) blend in the presence of nanosilica

The influence of nanosilica on the concentration fluctuation of polystyrene/poly (vinyl methyl ether) (PS/PVME) mixtures was investigated during phase separation. The amplitude of concentration fluctuation was quantified by dielectric spectrums based on the idea of Lodge–Mcleish model and the linearized Cahn–Hilliard theory could describe the amplitude evolution of concentration fluctuation at the early stage of phase separation. Hydrophilic nanosilica A200 dispersed in PVME‐rich phase behaved an obvious inhibition effect on the concentration fluctuation of blend matrix, while hydrophobic nanosilica R974 dispersed in PS‐rich phase had little effect on the concentration fluctuation. The kinetics and amplitude evolution of concentration fluctuation during phase separation for PS/PVME/A200 nanocomposites were remarkably restrained due to the surface adsorption of PVME on A200. As the segmental dynamics of PVME and PS in homogeneous matrix was hardly influenced by A200 and R974, the enhanced miscibility and the significantly constrained flow relaxation of PVME chains might contribute to the retarded concentration fluctuation of PS/PVME/A200 nanocomposites. While the weak interaction between R974 and components of blend matrix and little effect of R974 on the molecular dynamics of PS chains may result in the weak retardation of concentration fluctuation for blend matrix. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1337–1349     

Thermally induced phase separation of polystyrene-poly(vinyl methyl ether) mixtures

Past differential scanning calorimetry and dielectric relaxation measurements have established that polystyrene (PS)-poly(vinyl methyl ether) (PVME) mixtures exhibit a degree of compatibility when cast from toluene, whereas they are incompatible when cast from chloroform or trichloroethylene. The present study reports that toluene-cast mixtures can be phase-separated by thermal treatment at temperatures exceeding 125°C. This is true for samples containing 20–80 wt-% PS. The temperature of phase separation varies with heating rate; isothermal heating times needed to cause phase separation increase rapidly as the temperature approaches 125°C. Reversibility of the phase separation process depends upon such factors as cooling rate, annealing time, treatment temperature, and thermal history. By annealing and/or slow cooling, all thermally phase-separated mixtures have been brought back to their original state of compatibility. That is, there is no evidence for true irreversiblity of phase separation in thermally treated samples. Quench-cooled samples remain phase-separated indefinitely at room temperature, but this is attributed to rapid cooling below the glass transition of the PS. Chloroform-cast and trichloroethylene-cast mixtures have not been brought to a compatible state by thermal treatment, even after lengthy annealing and slow cooling steps.     

Stereoregularity of poly(vinyl ether)

α-Methylvinyl isobutyl and methyl ethers were polymerized cationically and the structure of the polymers was studied by NMR. Poly(α-methylvinyl methyl ether) polymerized with iodine or ferric chloride as catalyst was found to be almost atactic, whereas poly(α-methylvinyl isobutyl ether) polymerized in toluene with BF₃OEt₂ or AlEt₂Cl as catalyst was found to be isotactic. In both cases, the addition of polar solvent resulted in the increase of syndiotactic structure as is the case with polymerization of alkyl vinyl ether. tert-Butyl vinyl ether was polymerized, and the polymer was converted into poly(vinyl acetate), the structure of which was studied by NMR. A nearly linear relationship between the optical density ratio D₇₂₂/D₇₃₆ in poly(tert-butyl vinyl ether) and the isotacticity of the converted poly(vinyl acetate) was observed.     

Substitution and elimination reactions of poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether) using phase transfer catalysis

The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.     

Interaction of water with poly(vinyl methyl ether) in aqueous solution

Near-infrared, viscometric, and calorimetric measurements were made on aqueous poly(vinyl methyl ether) (PVME) solutions at temperatures between 15 and 43°C. We found a hydrogen-bonded structure of water around the polymer chain (a polymer-water complex), which is characterized by two distinct hydration numbers (i.e., 2.7 and 5.0 water molecules on each monomer unit of the chain) by analyzing the concentration dependence of endothermic enthalpies at a cloud point temperature, ca. 35°C. In particular, the 2.7 water-polymer complex has been suggested to be cooperatively formed by using data of the near-infrared (nir) absorption spectrum around 1930 nm. Furthermore, the peak-wavelength of the nir spectrum has been observed to change drastically at the cloud point when the temperature is raised. This can be interpreted as a cooperative collapse of the hydrogen-bonded water structure to free water, resulting in the aggregation of the polymer chains due to the exposure of their hydrophobic groups at the cloud point. © 1994 John Wiley & Sons, Inc.     

Precise synthesis of end‐functionalized thermosensitive poly(vinyl ether)s by living cationic polymerization

A series of poly(2‐methoxyethyl vinyl ether)s with narrow molecular weight distributions and with perfectly defined end groups of varying hydrophobicities was successfully synthesized by base‐assisting living cationic polymerization. The end group was shown to greatly affect the temperature‐induced phase separation behavior of aqueous solutions (lower critical solution temperature‐type phase separation) or organic solutions (upper critical solution temperature‐type phase separation) of the polymers. The cloud points were also influenced largely by the molecular weight and concentration of the polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Infrared study of poly(vinyl fluoride)

Poly(vinyl fluoride) polymers prepared at different polymerization temperatures have been examined in the melt, oriented, and solid state by infrared spectroscopy. Bands arising from the head-to-tail and head-to-head-tail-to-tail portions of the polymer have been isolated and assigned. The head-to-head-tail-to-tail portion of the polymer crystallizes in the head-to-tail unit cell except for a portion of the 1,2-difluorethylene units which apparently have the gauche (out-of-plane) structure. The head-to-tail portion of the polymer is nearly atactic, but is somewhat rich in syndiotactic chain structure. Bands arising from local syndiotactic order are observed.     

Condensed phase aromatization during degradation of poly(vinyl chloride)

Proton NMR results for partially degraded PVC show that aromatization accompanies dehydrochlorination in the condensed phase; subsequent fragmentation leads to loss of volatile aromatics.     

Heat capacity of poly(vinyl methyl ether)

The heat capacity of poly(vinyl methyl ether) (PVME) has been measured using adiabatic calorimetry and temperature‐modulated differential scanning calorimetry (TMDSC). The heat capacity of the solid and liquid states of amorphous PVME is reported from 5 to 360 K. The amorphous PVME has a glass transition at 248 K (?25 °C). Below the glass transition, the low‐temperature, experimental heat capacity of solid PVME is linked to the vibrational molecular motion. It can be approximated by a group vibration spectrum and a skeletal vibration spectrum. The skeletal vibrations were described by a general Tarasov equation with three Debye temperatures Θ₁ = 647 K, Θ₂ = Θ₃ = 70 K, and nine skeletal modes. The calculated and experimental heat capacities agree to better than ±1.8% in the temperature range from 5 to 200 K. The experimental heat capacity of the liquid rubbery state of PVME is represented by C_p(liquid) = 72.36 + 0.136 T in J K^?1 mol^?1 and compared to estimated results from contributions of the same constituent groups of other polymers using the Advanced Thermal AnalysiS (ATHAS) Data Bank. The calculated solid and liquid heat capacities serve as baselines for the quantitative thermal analysis of amorphous PVME with different thermal histories. Also, knowing C_p of the solid and liquid, the integral thermodynamic functions of enthalpy, entropy, and free enthalpy of glassy and amorphous PVME are calculated with help of estimated parameters for the crystal. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2141–2153, 2005