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71.
72.
The dissolution process of poly(methyl methacrylate), PMMA, in mixtures of the binary systems: acetonitrile/alcohol (methanol, ethanol and 1-propanol), individually poor and nonsolvents respectively for the polymer, was studied at 25 °C using FTIR imaging spectroscopy. To investigate this cosolvency phenomenon and the kinetics of the dissolution process, the spatial resolution and sensitivity of FTIR imaging were used. It has been found that the PMMA dissolution rate anomalously increases almost in a parabolic way independently of the solvent system used in this study. These results were interpreted assuming that the dissolution of a polymer by a mixture of solvents is governed by a complex dependence of the solvent molecules size and their thermodynamic characteristics. The kinetics of the PMMA dissolution by AcN/alcohol solvent mixtures were interpreted using conventional Arrhenius behavior in which the activation energy has a simple dependence on the thermodynamic quality and the molecular weight of the solvent mixture. 相似文献
73.
Interactions between the antioxidant Santonox (4,4′-thiobis(6-tert-butyl-m-cresol)) and the LCST polymer blend of polystyrene (PS) and polyvinylmethylether (PVME) were examined. The presence of the antioxidant caused inhomogeneities in blend films cast from toluene solutions at antioxidant compositions greater than 0.25 wt% of the PVME. Also, the cloud-point of the blend decreased linearly with antioxidant content with a slope of 21 °C/wt%. As expected, the ability of the antioxidant to prevent degradation of the PVME within the blend was found to increase with increasing Santonox composition. Based on these results, an antioxidant composition of no more than 0.10 wt% is recommended in the studies of PS/PVME blends. 相似文献
74.
Linear polyethers possess unusually high CO2 solubility and, hence, selectivity due to the presence of accessible ether linkages that can interact with the quadrupolar moment of CO2 molecules. In this work, membranes derived from crosslinked poly(propylene glycol) diacrylate (PPGda) oligomers differing in molecular weight (M), as well as PPGda nanocomposites containing either an organically-modified montmorillonite clay or a methacrylate-terminated fumed silica are investigated and compared with highly CO2-selective poly(ethylene glycol) diacrylate (PEGda) homopolymer and nanocomposite membranes previously reported. The rheological and permeation properties of PPGda depend sensitively on M, with the elastic modulus decreasing, but CO2 permeability and CO2/H2 selectivity increasing, with increasing M. Incorporation of either nanofiller into PPGda enhances the elastic modulus and reduces the gas permeability in the resultant nanocomposites without strongly affecting CO2/H2 selectivity. Blending PPGda and PEGda prior to chemical crosslinking yields binary membranes that exhibit intermediate gas-transport properties accurately described by a linear rule of mixtures. 相似文献
75.
The gel-size dependence of microphase separation in weakly-charged gels of N-isopropylacrylamide (NIPA) and 1-vinylimidazole (VI) copolymers has been investigated using swelling measurement, small-angle neutron scattering (SANS), and dynamic and static light scattering (DLS/SLS). It is known that weakly-charged polymer gels undergo microphase separation in a poor solvent as a result of competing interactions involving hydrophobic attraction versus electrostatic repulsion. The microphase separation is characterized by a scattering maximum in SANS intensity functions of which Bragg spacing, Λ, is around 20-30 nm. However, when gel size was reduced to the order of Λ, no microphase separation was observed. Instead, a typical scattering of isolated spherical particles was clearly observed. On the basis of the experimental evidence, we conclude that microphase separation has its own wavelength independent of gel size, and nanometer-order gels, i.e., nanogels, do not undergo microphase separation. 相似文献
76.
Justin R. Barone 《Chemical engineering science》2005,60(10):2579-2584
In this paper, spreading experiments on “heavy” polymer drops are performed. “Heavy” refers to large polymer drops, i.e., the radius of the drop, R, is much larger than the capillary length, κ-1, so that the spreading is dictated by gravity. The zero-shear viscosity can be found from measurements of the time-dependent drop radius or vice versa. Viscosity values found from spreading experiments compare well with the viscosity values found from dynamic rheological experiments. 相似文献
77.
78.
The conjugated effects of both reactive compatibilization and dynamic vulcanization on the phase inversion behavior of poly(butylene terephthalate) (PBT)/epoxide-containing rubber blends have been studied in detail. Pure ethylene-methyl acrylate random copolymer (E-MA) and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (E-MA-GMA) were used as non reactive or reactive rubber phase, respectively. Location of the phase inversion region was studied using several techniques, including transmission electron microscopy (TEM) and dynamical mechanical thermal analysis (DMTA). To evaluate the relative influence of the blend compatibilization and the dynamic vulcanization on the phase inversion behavior, the relative kinetics of the two reactions were modified using different PBT and E-MA-GMA grades. The obtained results show unambiguously that the position and the width of the phase inversion region is essentially governed by the kinetic of the dynamic vulcanization process. The effect of the blend compatibilization remains quite limited even in the case of fast interfacial reaction. The crosslinking of the rubber phase induces an important shift of the phase inversion composition to higher rubber content. For blends containing low molecular weight PBT, up to 60 wt% of rubber can be homogeneously dispersed in the PBT matrix at long mixing time. In this case, development of high performance PBT based thermoplastic vulcanisates can be envisioned. 相似文献
79.
The telomerization of dimethylaminoethyl methacrylate (DMAEMA) with mercaptoethanol initiated by 2,2′-azobisisobutyronitrile was first investigated at 70 °C and the influence of the type of solvent was studied. The results showed that well-defined telomers of DMAEMA could not be synthetized via telomerization of DMAEMA in water or water/acetonitrile mixture since the telomerization reaction is in competition with the nucleophilic addition of thiol onto the monomer. Transfer constants for mercaptoethanol in benzene and acetonitrile were determined by Mayo's and O'Brien's methods. The transfer constant obtained in acetonitrile (0,6) was higher than that obtained in benzene. This difference can be explained by the fact that the thiol was consumed by two reactions: nucleophilic addition and telomerization. The influence of solvents on the polymerization kinetics was enlightened. These results were applied to the synthesis of macromonomers of DMAEMA with isocyanatoethyl methacrylate (IEM). These macromonomers were copolymerized with styrene. 相似文献
80.
The phase behavior and motional mobility in binary blends of polystyrene (PS) and poly(cyclohexyl methacrylate) (PCHMA) have been investigated by solid state 13C NMR techniques. The blend miscibility has been studied by examining the 1H spin-relaxation times in the laboratory frame (T1H) and in the rotating frame (T1ρH) for the PCHMA/PS blends with various compositions and pure components. The T1ρH results show that PCHMA and PS are intimately mixed at the molecular level within the blends at all compositions. In addition, according to the results of carbon T1ρ relaxation time measurements, we conclude that mixing is intimate enough to cause a reduction in local chain mobility for PS, but an increase in side chain mobility for PCHMA. 相似文献