MISCIBILITY STUDIES OF POLY(ETHYLENE OXIDE)-POLY(VINYL ACETATE) BLENDS BY VISCOMETRY METHODS

The intrinsic viscosities of poly(ethylene oxide)-poly(vinyl acetate) blends (PEO-PVA) have been measured in chloroform as a function of molecular weights of blend components and compositions. The interaction parameters Delta b obtained from the modified Krigbaum and Wall theory and the differences between the intrinsic viscosities of polymer mixtures and the weight-average intrinsic viscosities of the two blend components were both used to characterize the extent of miscibility of the blend mixtures. (C) 1995 John Wiley and Sons, Inc.

DETERMINATION OF THE VINYL-ACETATE CONTENT IN ETHYLENE-VINYL ACETATE COPOLYMERS BY THERMOGRAVIMETRIC ANALYSIS

The dependence of thermal degradation behaviour on vinyl acetate (VA) content of ethylene-vinyl acetate (EVA) copolymers was studied by thermogravimetric analysis (t.g.a.). Among the parameters investigated, the maximum rate of weight loss at the stage of

THERMODYNAMICS OF POLY(ETHYLENE OXIDE)-POLY(VINYL ACETATE) BLENDS

Heat-of-mixing data, obtained on blends of poly(ethylene oxide) (PEO) with whole and fractionated poly(vinyl acetate) (PVAc), were used to feed Patterson's theory of polymer-polymer miscibility. Negative values of mixing enthalpy, contact-energy term, interaction'' parameter and excess volume were obtained only for blends with the lowest molecular weight PVAc fraction. These results show that miscibility of PVAc with PEO strongly depends on its molecular weight. The calculated unfavourable excess volume term of the Patterson equation is small in comparison with the absolute value of the interaction term. Therefore, miscibility of PEO and low-molecular-weight PVAc is dictated by the weak specific interactions between different repeat units and by the entropic gain in the mixing process.

BLENDS OF POLY[3,3-BIS(CHLOROMETHYL)OXETANE] WITH POLY(VINYL ACETATE) .1. THERMAL AND MECHANICAL-PROPERTIES

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T(g)). The T(g) of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a beta-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations.

MUTUAL ENTANGLEMENTS IN POLY(VINYL ACETATE) POLY(METHYL ACRYLATE) INTERPENETRATING POLYMER NETWORKS

An equation has been derived for the equilibrium swelling of sequential interpenetrating polymer networks (IPNs), which exhibit a single glass transition temperature and the two components are considered to be compatible. The properties of the equilibrium swelling and elastic modulus of sequential poly(vinyl acetate)/poly(methyl acrylate) IPNs have been discussed according to the derived equation and the Siegfried-Thomas-Sperling formula of the elastic modulus for homo IPNs. In both fully swollen and bulk states, there was favourable evidence for added physical crosslinks in poly(vinyl acetate)/poly(methyl acrylate) IPNs. The Binder-Frisch theory is also discussed.

DYNAMIC SCALING OF THE STRUCTURE-FUNCTION FOR SPINODAL DECOMPOSITION IN CRITICAL AND NONCRITICAL MIXTURES OF POLY(VINYL ACETATE) POLY(METHYL METHACRYLATE)

The dynamics of phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by using a time-resolved light-scattering technique. In the later stages of spinodal decomposition, a simple dynamic scaling law was found for the scattering function S(q, t)(S(q, t) approximately I(q, t)): S(q, t)q(m)-3 S approximately (q/q(m)). The scaling function determined experimentally was in good agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X8) for critical concentration, and approximately in agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X6) for non-critical mixtures. The light-scattering invariant shows that the later stages of the spinodal decomposition were undergoing domain ripening.

MISCIBILITY OF POLY(EPICHLOROHYDRIN) WITH POLY(VINYL ACETATE) AND POLY(STYRENE-CO-ACRYLONITRILE)

The phase behaviours of poly(vinyl acetate) (PVAc) and poly(styrene-co-acrylonitrile)s (SAN) with poly(epichlorohydrin) (PECH) were examined using differential scanning calorimetry and an optical method using a hot plate. The PECH/PVAc blends showed LCST behaviour. The observed miscibility is thought to be a result of hydrogen-bonding interactions between the alpha-hydrogen atoms of PECH and the carbonyl groups of PVAc. Two SAN copolymers with an acrylonitrile (AN) content of 18 wt% (SAN18) and 25 wt% (SAN25), respectively, were also found to exhibit miscibility with PECH. No phase separation occurred by heating up to about 280-degrees-C, and the individual blend has a single, composition-dependent glass transition temperature. The formation of miscible PECH/SAN blends can be considered as a result of the intramolecular repulsion between styrene and AN units in SAN.

Pre-column derivatization of amines with 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate followed by LC-fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCl-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH](+) under APCl in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of l(BCIC)/l(CEOC) and l(BCIC)/l(FMOC) are, respectively, 1.23-3.14 and 1.25-3.08 for fluorescent (FL) responses (here, l is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6-37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV < 7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997.

Development of a LCST membrane forming system for cellulose acetate ultrafiltration hollow fiber

A novel lower critical solution temperature (LCST) membrane forming system containing cellulose acetate (CA)/poly (vinyl pyrrolidone) (PVP 3 60K)/N-methyl-2-pyrrolidone (NMP)/1,2-propanediol with a weight ratio of 24.0:5.0:62.6:8.4 had been developed. CA hollow fiber ultrafiltration (UF) membranes were fabricated using the dry-wet spinning technique. The fibers were post-treated with a 200 mg/L hypochlorite solution over a period of 6 It at pH 7. The experimental results showed that water flux of a membrane decreased while retention increased with increasing CA concentration in a dope. It was concluded that the membrane pore size decreased with increasing CA concentration. The membrane fouling tendency for BSA was 3 times higher than that for PVP 24K. (C) 2004 Elsevier B.V. All rights reserved.