Unexpected Stress Overshoot in Extensional Flow of Star Polymer Melts.

Previous studies have shown that the nonlinear rheological behavior of 3-arm star polymer melts in fast extensional flow is identical to that of linear polymers with the same span molecular weight, because the star polymers are highly aligned and have a similar conformation as the corresponding linear polymers. However, with more arms, it would be more difficult for the stars to be aligned like linear chains, and the nonlinear extensional rheology of star polymers with more arms under large deformations has not been investigated yet. Here we show that the star polystyrene (8-10 arms) melts behave differently from the linear polystyrenes. A transient stress overshoot is observed in the fast extensional flow, probably due to the difference in entanglement density near and far away from the branch point.

Predicting maximum strain hardening factor in elongational flow of branched pom-pom polymers from polymer architecture.

We present a model-driven predictive scheme for the uniaxial extensional viscosity and strain hardening of branched polymer melts, specifically for the pom-pom architecture, using the small amplitude oscillatory shear mastercurve and the polymer architecture. A pom-pom shaped polymer is the simplest architecture with at least two branching points, needed to induce strain hardening. It consists of two stars, each with q arms of the molecular weight M w , a , connected by a backbone of M w , b . Despite the pom-pom constitutive model, experimental data of systematic investigations lack due to synthetic complexity. With an optimized approach, we synthesized polystyrene pom-pom model systems with systematically varied M w , a and M w , b . Experimentally, we identify four characteristic strain rate dependent regimes of the extensional viscosity, which can be predicted from the rheological mastercurve. Furthermore, we find that the industrially important maximum strain hardening factor depends only on the arm number by [ q 2 / ln ( 3 q ) ] . This framework offers a model-based design of branched polymers with predictable melt flow behavior.

Fast and Scalable Synthetic Route to Densely Grafted, Branched Polystyrenes and Polydienes via Anionic Polymerization Utilizing P2VP as Branching Point.

Defined, branched polymer architectures with low dispersity and architectural purity are of great interest to polymer science but are challenging to synthesize. Besides star and comb, especially the pom-pom topology is of interest as it is the simplest topology with exactly two branching points. Most synthetic approaches to a pom-pom topology reported a lack of full control and variability over one of the three topological parameters, the backbone or arm molecular weight and arm number. A new, elegant, fast, and scalable synthetic route without the need for post-polymerization modification (PPM) or purification steps during the synthesis to a pom-pom and a broad variety of topologies made from styrene and dienes is reported, with potential application to barbwire, bottlebrush, miktoarm star, Janus type polymers, or multi-graft copolymers. The key is to inset short poly(2-vinyl-pyridine) blocks (<2 mol% in the branched product) into the backbone as branching points. Carb anions can react at the C6 carbon of the pyridine ring, grafting the arms onto the backbone. Since the synthetic route to polystyrene pom-poms has only two steps and is free of PPM or purification, large amounts of up to 300 g of defined pom-pom structures can be synthesized in one batch.

Magnesium Polymer Electrolytes Based on the Polycarbonate Poly(2-butyl-2-ethyltrimethylene-carbonate).

Magnesium electrolytes based on a polycarbonate with either magnesium tetrakis(hexafluoroisopropyloxy) borate (Mg(B(HFIP)4)2) or magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) for magnesium batteries were prepared and characterized. The side-chain-containing polycarbonate, poly(2-butyl-2-ethyltrimethylene carbonate) (P(BEC)), was synthesized by ring opening polymerization (ROP) of 5-ethyl-5-butylpropane oxirane ether carbonate (BEC) and mixed with Mg(B(HFIP)4)2 or Mg(TFSI)2 to form low- and high-salt-concentration polymer electrolytes (PEs). The PEs were characterized by impedance spectroscopy, differential scanning calorimetry (DSC), rheology, linear sweep voltammetry, cyclic voltammetry, and Raman spectroscopy. A transition from classical salt-in-polymer electrolytes to polymer-in-salt electrolytes was indicated by a significant change in glass transition temperature as well as storage and loss moduli. Ionic conductivity measurements indicated the formation of polymer-in-salt electrolytes for the PEs with 40 mol % Mg(B(HFIP)4)2 (HFIP40). In contrast, the 40 mol % Mg(TFSI)2 PEs showed mainly the classical behavior. HFIP40 was further found to have an oxidative stability window greater than 6 V vs Mg/Mg2+, but showed no reversible stripping-plating behavior in an Mg||SS cell.

One-Pot Synthesis of Alternating (Ultra-High Molecular Weight) Multiblock Copolymers via a Combination of Anionic Polymerization and Polycondensation.

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.