Physical ageing in poly(vinyl acetate) 1. Enthalpy relaxation

The enthalpy changes ΔH_∞ between a poly(vinyl acetate) glass formed by rapid cooling and the corresponding fully relaxed glass have been estimated at four temperatures below the glass transition. The values obtained were different to those expected by extrapolating liquid behavior below the glass transition and were found to agree well with the predictions of a simple expression for the combined main chain conformational and free volume contributions to enthalpy. Conformational contributions from the side chain alone were also considered but were not required to obtain agreement with experiment. It can be concluded that the side chains remained mobile below the glass transition and do not contribute to the heat capacity discontinuity at T_g. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1107–1116, 1997     

Cationic polymerization behavior of seven-membered cyclic sulfite

Cationic ring-opening polymerization behavior of a seven-membered cyclic sulfite ( 1 ) was examined. 1 was prepared by the reaction of 1,4-butanediol with SOCl₂ in 58% yield. The cationic polymerization of 1 was carried out at 0, 25, 60, or 100°C with trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), BF₃ · OEt₂, SnCl₄, methyl p-toluenesulfonate (TsOMe), or MeI as an initiator in bulk under a nitrogen atmosphere to afford the polymer with M̄_n 1000–10,400. The order of activities of the initiators for 1 was as follows, TfOH ≅ TfOMe > SnCl₄ > BF₃ · OEt₂ > TsOMe ≅ MeI. The polymerization of 1 with TfOMe afforded a poly(sulfite) below 25°C, but afforded a polymer containing an ether unit at 60°C, which was formed by a desulfoxylation. The higher the activity of the initiator was, the more easily the desulfoxylation occurred. We expected volume expansion on polymerization because cyclic sulfites have large dipole moment values, but it turned out that 1 showed 4.34% shrinkage on polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3673–3682, 1997     

Density and viscosity of 1-butyl-3-methylimidazolium nitrate with ethanol, 1-propanol, or 1-butanol at several temperatures

Densities and viscosities of 1-butyl-3-methylimidazolium nitrate [Bmim][NO₃], and its binaries with alcohol (ethanol, 1-propanol, or 1-butanol) were measured at different temperatures. The densities and viscosities of pure ionic liquid were correlated successfully by empirical equations. The Vogel–Fulcher–Tammann equations can fit the experimental data of viscosities for pure IL. Excess molar volume and viscosity deviations were calculated for the binaries. The excess molar volumes have negative deviations from the ideal solution.     

Prediction of sensory properties of Brazilian Arabica roasted coffees by headspace solid phase microextraction-gas chromatography and partial least squares

Volatile compounds in fifty-eight Arabica roasted coffee samples from Brazil were analyzed by SPME-GC-FID and SPME-GC-MS, and the results were compared with those from sensory evaluation. The main purpose was to investigate the relationships between the volatile compounds from roasted coffees and certain sensory attributes, including body, flavor, cleanliness and overall quality. Calibration models for each sensory attribute based on chromatographic profiles were developed by using partial least squares (PLS) regression. Discrimination of samples with different overall qualities was done by using partial least squares-discriminant analysis (PLS-DA). The alignment of chromatograms was performed by the correlation optimized warping (COW) algorithm. Selection of peaks for each regression model was performed by applying the ordered predictors selection (OPS) algorithm in order to take into account only significant compounds. The results provided by the calibration models are promising and demonstrate the feasibility of using this methodology in on-line or routine applications to predict the sensory quality of unknown Brazilian Arabica coffee samples.According to the PLS-DA on chromatographic profiles of different quality samples, compounds 3-methypropanal, 2-methylfuran, furfural, furfuryl formate, 5-methyl-2-furancarboxyaldehyde, 4-ethylguaiacol, 3-methylthiophene, 2-furanmethanol acetate, 2-ethyl-3,6-dimethylpyrazine, 1-(2-furanyl)-2-butanone and three others not identified compounds can be considered as possible markers for the coffee beverage overall quality.     

Advantages of a small-volume counter-current chromatography column

Counter-current chromatography (CCC) works with a support-free liquid stationary phase. This allows for preparative separations and purifications. However, there are serious technical constraints because of the need to keep a liquid stationary phase in a column. Centrifugal fields are used. A new commercial hydrodynamic 18 mL column made with a narrow-bore 0.8 mm Teflon tubing was evaluated by comparing it with older hydrodynamic CCC columns and a similar 19 mL column but made with 1.6 mm Teflon tubing. A small-volume CCC column allows for reliable and fast solute partition coefficient determination. When resolution is required, both high efficiency and liquid stationary phase retention are needed. Unfortunately, these two requirements bear technical contradictions. A column coiled with a narrow tubing bore will provide a high chromatographic efficiency while a column containing wider tubing bore will achieve higher stationary phase retention. In all cases, increasing the magnitude of the centrifugal field also increases the stationary phase retention. The solution is to build centrifuges able to produce high fields that will provide acceptable liquid phase retention with narrow-bore tubes. The new 18 mL 0.8 mm tubing bore column is able to rotate as fast as 2100 rpm generating a 240 × g field. The two older CCC columns cannot compete with the new one. However, the small 19 mL column with 1.6 mm bore tubing can be useful when fast results are desired without top resolution.     

Dual-purpose gas chromatographic injection device for pressurized liquid and gas injection

A dual-purpose gas chromatographic injection device, capable of injecting pressurized liquid sample of up to 5000 psig and gas sample with a volume as high as 5000 μL, has been successfully developed and implemented. The injection device is synergized by the effectiveness of a classical flash vaporization of a syringe injection and the reliability of a proven rotary valve. Depending on the matrix involved, this injection device employs either a commercially available four-port internal valve for liquid sampling or a six-port external valve for gas sampling, a modified removable needle used in standard liquid syringe, and an auxiliary flow stream that can be either mechanical or electronic flow controlled for solute transfer. For pressurized liquid, the device was found suitable of up to nC₁₆ hydrocarbon with no observable carry-over despite the injection device was operating at ambient temperature. A relative standard deviation of less than 2% (n = 20) was obtained for hydrocarbon compounds ranging from nC₈ to nC₁₆. For gas injection, the device performed well even under difficult chromatographic conditions such as with a low column inlet pressure of less than 1 psig. A relative standard deviation of less than 0.5% (n = 10) was obtained for reactive sulfur compounds such as alkyl mercaptans. The device can be operated manually or automated with pneumatic or electrical actuator, is platform neutral, and can be moved amongst instruments without hardware modification as well as implemented for on-line or in situ applications. In this paper, the utility of the device was also demonstrated with selected GC applications of industrial significance.     

Measurement of ternary polymer/solvent equilibrium data by vapor-phase infrared spectroscopy

Vapor–liquid equilibrium (VLE) data for binary toluene/PVAC, methanol/PVAC and ternary toluene/methanol/PVAC systems have been measured at 100 °C by using vapor-phase infrared spectroscopy. Binary data have been compared with literature data measured by different experimental techniques and agreement between our measurements and others was found to be good. The ternary VLE data indicate that the solubility of methanol in PVAC is not influenced by the presence of toluene, while the solubility of toluene is lowered due to presence of methanol. To predict ternary VLE data, the Entropic free volume and Kannan free volume models and the Flory-Huggins theory were used. The predictive abilities of Flory-Huggins theory and the Kannan free volume model are similar and better than that of the Entropic free volume model.