SynopsisMelt polymerization conditions for D,Llactide initiated with tetraphenyltin were studied with regard to polymer molecular weight and weight distributions. "Single" polymerization, "multiple" polymerization (four or eight reactions a t the same time), and timedependent 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.
A~traet--Intrinsic viscosities [7] of poly(2,6-dimethyl-l,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 [r/]-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 ~,f and the solvent draining over the whole temperature interval, a slight increase of characteristic parameter C~ with decreasing temperature has been calculated.
Sedimentation and flotation coefficients of poly(2,6-dimethyl-l,4-phenylene oxide) (PPO) solutions have been measured as a function of temperature between 60 and 25. The solvents were toluene and trichloroethene (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 parameter ¢'o.
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