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.

Molecularly Defined Polyolefin Vitrimers from Catalytic Insertion Polymerization.

Vitrimers can combine the advantageous properties of cross-linked materials with thermoplastic processability. For the prominent case of polyethylene, established post-polymerization introduction of cross-linkable moieties results in extremely heterogeneous compositions of the chains. Here, we report the generation of functionalized polyethylenes directly by catalytic insertion polymerization, with incorporated cross-linkable aryl boronic esters or alternatively acetal-protected groups suited for cross-linking with difunctional boronic esters. In addition to the desired homogeneous in-chain distribution, the reactive cross-linkable groups are enriched at the chain ends. This enables the incorporation of all chains in the network, as also supported by simulations of all chains' compositions. The uniform molecular composition of the chains reflects in resulting vitrimers' material properties, particularly lack of leaching with solvents. At the same time, cross-linking is indeed fully reversible and the vitrimers can be recycled.

Phosphine-functionalised tris(pyrazolyl)methane ligands and their mono- and heterobimetallic complexes.

The synthesis, characterisation and reactivity of new phosphine-functionalised tris(pyrazolyl)methane ligands (TpmPR2, 2a-c, with R = Ph, nBu, iPr) are presented. The reaction of 2a-c with [Rh(CO)2Cl]2 furnished N,P-heterochelate carbonyl complexes (3a-c), which were used to quantify the donor abilities of the ligands via IR spectroscopy. The coordination flexibility was demonstrated by treating representative members of this new ligand class with [CpRu(acn)3][PF6] (acn = acetonitrile), [(tht)AuCl] (tht = tetrahydrothiophene) and [Pd(allyl)Cl]2 providing either a N,N,P-heteroscorpionate complex (4) or the P-coordinated complexes (5,6) without any involvement of the pyrazolyl entities. With 2a and [Pd(cod)Cl2], another P,N-heterochelate complex (7) was obtained, which served as a precursor for a heterobimetallic complex containing palladium and copper (8). Detailed NMR spectroscopic and X-ray crystallographic investigations have been performed on all new complexes.