Linearized cloudpoint curve correlation for ternary systems consisting of one polymer, one solvent and one non-solvent

A linear correlation function is found for cloudpoint composition curves of ternary systems consisting of one polymer, one solvent and one non-solvent. The conditions for validity of this correlation function appear to be that the polymer is strongly incompatible with the non-solvent, and that only liquid-liquid demixing occurs. The linearized cloudpoint (LCP) curve is interpreted in terms of the various parameters occurring in the Flory-Huggins theory. The slope of the LCP line appears to be only dependent on the molar volumes of the components. Information about the binary Flory-Huggins interaction parameters and their concentration dependence can be obtained from the intercept of the linearized curve. Cloudpoints induced by crystallization do not follow the correlation. This gives an opportunity to distinguish between crystallization and liquid-liquid demixing without any additional experiments

Conformational behaviour of poly(2,6-dimethyl-1,4-phenylene oxide) in solution - I: Intrinsic viscosity as a function of temperature

Intrinsic viscosities [η] of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) solutions have been measured as a function of temperature between 60 and 25°C. The solvents were toluene and trichloroethene. In both solvents, the [η]-T curve exhibited a point of inflection in the range 45-35°. This phenomenon is explained as a conformational transition, which is possibly involved in the nucleation process of the solution crystallization of PPO. Assuming constancy of the coil expansion factor αη and the solvent draining over the whole temperature interval, a slight increase of characteristic parameter Cα, with decreasing temperature has been calculated

Conformational behaviour of poly(2,6-dimethyl-1,4-phenylene oxide) in solution - II. Sedimentation coefficients and permeabilities in the semi-dilute region as a function of temperature

Sedimentation and flotation coefficients of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) solutions have been measured as a function of temperature between 60 and 25°. The solvents were toluene and trichloroethane (TCE). Solvent permeabilities have been calculated from the sedimentation or flotation coefficients. PPO is less permeable to the solvents used than polystyrene of comparable molecular weight is to toluene and cyclohexane. Strong solvation of toluene and TCE by PPO molecules is proposed as an explanation for this finding. The measured permeabilities were used to check an earlier calculation of the change of radius of gyration with temperature from intrinsic viscosity data. A larger decrease in radius of gyration with increasing temperature has been calculated in this way than with the earlier assumption of essentially impermeable polymer coils, i.e. with the assumption of the value 2.5 × 1023 for the universal viscosity paramete

Phase separation processes in polymer solutions in relation to membrane formation

This review covers new experimental and theoretical physical research related to the formation of polymeric membranes by phase separation of a polymer solution, and to the morphology of these membranes. Two main phase separation processes for polymeric membrane formation are discussed: thermally induced phase separation and immersion precipitation. Special attention is paid to phase transitions like liquid-liquid demixing, crystallization, gelation, and vitrification, and their relation to membrane morphology. In addition, the mass transfer processes involved in immersion precipitation, and their influence on membrane morphology are discussed

Metastable liquid-liquid and solid-liquid phase boundaries in polymer-solvent-nonsolvent systems

In general liquid-liquid demixing processes are responsible for the porous morphology of membranes obtained by immersion precipitation. For rapidly crystallizing polymers, solid-liquid demixing processes also generate porous morphologies. In this study, the interference of both phase transitions has been analyzed theoretically using the Flory-Huggins theory for ternary polymer solutions. It is demonstrated that four main thermodynamic and kinetic parameters are important for the structure formation in solution: the thermodynamic driving force for crystallization, the ratio of the molar volumes of the solvent and the nonsolvent, the polymer-solvent interaction parameter, and the rate of crystallization of the polymer compared to the rate of solvent-nonsolvent exchange. An analysis of the relevance of each of these parameters for the membrane morphology is presented

The ring-opening polymerization of D,L-lactide in the melt initiated with tetraphenyltin

Melt polymerization conditions for D,L-lactide initiated with tetraphenyltin were studied with regard to polymer molecular weight and weight distributions. "Single" polymerization, "multiple"polymerization (four or eight reactions at the same time), and time-dependent studies are described. Single polymerizations using constant initiator concentrations resulted in a broad scattering of nonreproducible molecular weight values. Multiple polymerizations at constant initiator concentrations, however, resulted in nearly identical molecular weight profiles. Multiple polymerizations at different initiator concentrations did not show an inverse dependency of initiator concentration on polymer molecular weight. Both the single and multiple melt polymerizations resulted in rather broad molecular weight distributions. The presence of hydrolysis products of lactide during the melt polymerization most likely has a detrimental effect on molecular weight. After a short induction period the rather slow polymerization of D,L-lactide resulted in a maximal molecular weight followed by a slight decrease in molecular weight to a constant value. It is concluded that the polymerization of D,L-lactide in the melt initiated with tetraphenyltin does not proceed through a "living" mechanism

Correction of flotation coefficients, derived from ultracentrifugation, for pressure and concentration

Flotation coefficients are usually determined from data obtained under high pressure (cell bottom) conditions. A power series expansion is proposed for correction to atmospheric pressure (meniscus) conditions. The same expansion may be applied to the concentration correction of flotation coefficients

Phase transitions during membrane formation of polylactides. I. A morphological study of membranes obtained from the system polylactide-chloroform-methanol

The influence of solid-liquid demixing, liquid-liquid demixing and vitrification on the morphology of polylactide membranes has been investigated. To study the effects of crystallization of polylactides on the membrane and morphology, polylactides of varying stereoregularity were used. The polymers applied were poly--lactide (PLLA) and copolymers with different molar ratios of -lactide and -lactide [poly-L95/D5-lactide (PLA95), poly-L80/D20-lactide (PLA80) and poly-L50/D50-lactide (PDLLA)]. Solutions of polylactides in chloroform cast on a glass plate were immersed in methanol. From solutions containing the slowly crystallizing PLA80 or uncrystallizable PDLLA porous membranes were obtained if the phase separated system was removed from the nonsolvent bath within a few hours after immersion. After longer equilibration times in methanol the structure collapsed. The swelling in the nonsolvent methanol was too high to allow stabilization of the liquid-liquid demixed structure by vitrification. Stable membranes were easily obtained with more rapidly crystallizing polymers like PLLA. Casting solutions with low PLLA concentrations gave membranes with a cellular morphology due to liquid-liquid demixing by nucleation and growth of a polymer poor phase. Crystallization only played a role in the fixation of the liquid-liquid demixed structure. At increasing PLLA concentrations the demixing sequence gradually reversed to crystallization followed by liquid-liquid demixing. In these cases membranes with porous spherulites or spherulites surrounded with a cellular layer were obtained