Poly(vinylidene fluoride) (PVDF) experimental samples containing sparsely distributed chain branching were compared to commercial reference samples. The results showed a lower onset of shear thinning for the branched samples over the reference counterparts. The storage modulus of the branched samples at low frequency shows a significant increase for the low-molecular weight sample while the higher-molecular weight sample showed a moderate increase suggesting a strong contribution of chain branching. The branched PVDF samples exhibited a lower radius of gyration (R G ) and intrinsic viscosity than the commercial samples over the entire molecular weight range. NMR revealed the presence of tertiary carbons, suggesting that the branches are covalently bonded and not of a physical nature. Extensional viscosity data showed that the branched samples display a significant degree of strain hardening while the reference samples exhibit a small degree of strain hardening.

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In this work the effect of strain hardening on poly-vinylidene fluoride (PVDF) extrusion blown film is investigated. Controlled long chain branching is introduced via a multi-functional initiator to produce two PVDF samples with different molecular weight and chain architecture. The branched samples are compared to two reference resins having identical molecular weight and no chain branching. All samples are characterized by size exclusion chromatography (SEC) coupled with triple detection system comprising a Differential Refractive Index (DRI) detector, Intrinsic Viscosity (IV) detector, and Multi-Angle Laser Light Scattering (MALLS) detector, to determine their molecular weights and their distribution as well as to detect chain branching via measuring the coil size in dilute solution. The rheological properties are determined using oscillatory measurement and melt strength at 230°C while extensional viscosity measurements are conducted at 180°C to determine strain hardening at different extension rates. The resins are evaluated using a small scale extrusion blown film set-up to determine the blow-up ratio and the minimum thickness achievable. The characterization results show that the control samples are different in molecular weight and almost identical in the polydispersity index (Mw/Mn). The branched samples, however, have higher molecular weight and a slightly broader molecular weight distribution. Light scattering data together with inherent viscosity data show that the branched samples have a lower radius of gyration (RG) and inherent viscosity (IV) over the entire molecular weight distribution confirming chain branching. The rheological properties in oscillatory measurements show that the branched samples exhibit almost identical viscosities as the control samples. However, a broader transition from the Newtonian to the non-Newtonian region for the branched sample is observed confirming the SEC—MALLS results. This is corroborated using extensional viscosity and melt strength measurements, which show a significant strain hardening and an increase in melt strength, respectively. Blown film experiments show that the samples containing chain branching could be processed under similar process conditions as the control samples, and with a higher blow up ratio thereby achieving 5 μm film thickness with high clarity.

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The kinetics of the reaction between alkaline sulfides and halogenated aromatic monomers was studied using lithium sulfide and 4-chlorobenzophenone (1 a) and 4,4'-dichlorobenzophenone (1 b) as models. The release of H2S from reaction medium and the possible formation of a compound between sulfide and N-methyl-2-pyrrolidone (NMP) during the preliminary dehydration step are key steps of the reaction. The reaction proceeds following two successive kinetic regimes: a first one where rapid second-order reactions of sulfide and thiolate with 1 a or 1 b take place, and a second one where the slow release of sulfide from the compound formed during dehydration is rate determining and therefore governs the molecular weight of final polymer. A good agreement was found between theoretical curves calculated from this kinetic scheme and experimental data, indicating a polymerization mechanism based on an SNAr reaction mechanism.

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