The extrusion flow instabilities of two commercial styrene‐butadiene rubbers are investigated as they vary in isomer content (1,4‐cis, 1,4‐trans, and 1,2 conformation) of the butadiene monomer and the molecular architecture (linear, branched). The investigated samples have similar multimodal molecular weight distribution. Two geometries of extrusion dies, slit and round capillary, are compared in terms of the type and the spatial characteristics of the flow instabilities. The latter are quantified using three methods: a highly pressure sensitive slit die, online and offline optical analysis. The highly pressure‐sensitive slit die has three piezoelectric pressure transducers (Δt ≈ 10−3 s and Δp ≈ 10−5 bar) placed along the die length. The characteristic frequency (fChar.) of the flow instabilities follows a power law behavior as a function of shear rate to a 0.5 power for both materials,  fChar.∝trueγ˙app.0.5. A qualitative model is used to predict the spatial characteristic wavelength (λ) of the flow instabilities from round capillary to slit dies and vice versa. Slip velocities (Vs) are used to quantify the slippage at slit and round capillary dies as well.

The development of sophisticated synthetic routes for polymeric materials and more complex formulation used in current polymers require more advanced analytical techniques. A direct correlation between molar mass distribution and chemical composition is provided.

A state-of-the-art, medium-resolution H-NMR spectrometer (62 MHz) is used as a chemically sensitive online detector for size-exclusion chromatography of polymers such as polymethylmethacrylate (PMMA) and polystyrene (PS). The method uses protonated eluents and works at typical chromatographic conditions with trace amounts of analytes (<0.5 g L after separation). Strong solvent suppression, e.g., by a factor of 500, is achieved by means of T -filtering and mathematical subtraction methods. Substantial improvements are made with respect to previous work in terms of the sensitivity (signal-to-noise ratio up to 130:1, PMMA OCH ) and selectivity (peak width, full width half maximum (FWHM) 4 Hz on-flow). Typical homopolymers and a blend are investigated to deformulate their composition along the dimensions of molecular weight and NMR chemical shift. These results validate this new hyphenated chromatography method, which can greatly facilitate analysis and is much more effective than previously published results.

The extrusion flow instabilities of three commercial styrene-butadiene rubbers (SBR) are investigated as a function of molecular weight distribution (MWD); molecular architecture (linear, branched); and temperature. The samples have multimodal MWD, with the main component being SBR and a low amount, less than 10 wt. %, of low-molecular weight hydrocarbons. Deviation from the Cox–Merz rule at high angular frequencies/shear rates becomes intense as the amount of medium-molecular weight component increases. Optical analysis is used to identify and quantify spatial surface distortions, specifically wavelength (λ) and height (h), of the different types of extrusion flow instabilities. Qualitative constitutive models are reviewed and used to fit the experimental data for the spatial characteristics of extrusion flow instability. The fitting parameters as obtained by the models are correlated with molecular properties of the materials. It is found that the characteristic spatial wavelength (λ) increases as the extrusion temperature decreases. Hence, the influence of temperature on the spatial characteristic wavelength is investigated and an Arrhenius behavior is observed.

This article presents a fast, straightforward synthesis approach to polymerize alternating multiblock copolymers, ultra-high molecular weight (UHMW) (homo)polymers as well as precursors for complex macromolecular topologies such as comb or barbwire architectures. The one-pot synthesis strategy proposed in this work is based on anionic polymerization via a bifunctional initiator and the subsequent linking of macro dianions with a bifunctional linker, additionally overcoming the limitations associated with the monomer reactivity. Thus, the synthetic route guarantees the repeating size of polymer blocks and an equal distribution of functional groups in precursors for complex topologies. Dianions of polystyrene ( PS), polyisoprene-b-polystyrene-b-polyisoprene, and poly-2-vinylpyridine-b-polystyrene-b-poly-2-vinylpyridine are linked with 𝜶, 𝜶 ′ -dibromo-para-xylene to UHMW and multiblock copolymers. Multiblock copolymers with on average up to 50 well-defined alternating A and B blocks are accessible within 15 min.