Liquid/Liquid Demixing in the System n-Hexane/Narrowly Distributed Linear Polyethylene
Demixing conditions were measured visually for solutions of three narrowly distributed polyethylene samples (M ranging from 6.5 to 380 kg/mol) in n-hexane up to 500 K and 150 bar. This information yields the critical line for infinite molar mass; i.e., it specifies the pT area within which one is safe from phase separation irrespective of the molar mass of the polymer and of the composition of the mixture. The experimental findings are in good qualitative agreement with the predictions of the Sanchez−Lacombe theory applied without any adjustable parameters. The influences of molar masses are, however, underestimated, and the resulting critical compositions are too small. For a more quantita…
Isobornyl Methacrylate as a Reactive Solvent of Polyethylene
Solutions containing 15 wt, -% of a low-molar-mass polyethylene (PE) in isobornyl methacrylate (IBoMA), containing 0, 5 or 10 wt.-% of 1,4 butanediol dimethacrylate (BDDMA) as crosslinker, were polymerized using either benzoyl peroxide (BPO), at 80°C, or dicumyl peroxide (DCPO), with a thermal cycle attaining 150°C, as initiators. Phase separation of an amorphous PE-rich phase took place when carrying out the reaction at temperatures higher than the PE melting temperature. Partial crystallization of PE was observed when cooling to room temperature. Depending on the initial amount of BDDMA, the fraction of PE that was phase separated varied between 57 and 66% of the initial amount, with crys…
Cluster formation and rheology of photoreactive nanoparticle dispersions.
We show how photocrosslinking of small nanoparticles within a very dilute colloidal dispersion leads to the formation of large fractal particle clusters, which have a strong influence on the viscosity of the dispersion although the overall solid content is well below 5 wt %. Furthermore, the solvent plays an important role because of its function as an optical filter, for example, in toluene only photocrosslinking but no photocleavage takes place. Therefore, a diffusion-controlled cluster growth mechanism, leading to clusters with low fractal dimension, is expected; on the other hand, in tetrahydrofuran the photoreaction is partially reversible. Therefore, the cluster growth in this case is…
Excess viscosity and glass transition
Abstract Literature data on the viscosity of solutions of poly(butyl methacrylate) (PBMA) and poly(methyl methacrylate) (PMMA) in diethyl phthalate (DEP) for different temperatures, including the range around and below T g , the glass transition temperatures of the pure polymers, were evaluated by means of an approach that uses surface fractions as composition variables. The discussion of these results together with information on solutions of the isomeric polymers, poly(vinyl acetate) (PVAc) and poly(methyl acrylate) (PM(A)), in the same solvent testifies that the previously published relations remain valid for T T g . They enable the determination of viscosities of the pure polymers below…
Molecular surfaces: An advantageous starting point for the description of composition-dependent viscosities applied to polymer solutions
The viscosity of polymer/solvent systems is modeled as a function of composition under the premises that the dissipation of energy is taking place at the molecular interfaces and that the friction between solvent and solute varies with composition due to a change in the flow mechanism (drainage of coils). The simple expression obtained in this manner contains three system-specific parameters: a geometric factor γ, which accounts for the differences of the surface to volume ratios of the components; a hydrodynamic parameter α, which measures the friction between solute and solvent in the case of fully draining polymer coils; and β, which corrects for changes in the friction between unlike mo…