Tapered Multiblock Copolymers Based on Isoprene and 4-Methylstyrene: Influence of the Tapered Interface on the Self-Assembly and Thermomechanical Properties

The synthesis of tapered multiblock copolymers by statistical living anionic copolymerization of a mixture of isoprene (I) and 4-methylstyrene (4MS) in cyclohexane is based on vastly different reac...

Myrcenol-Based Monomer for Carbanionic Polymerization: Functional Copolymers with Myrcene and Bio-Based Graft Copolymers

A bio-based hydroxyl group-containing diene monomer, silyl-protected β-myrcenol (MyrOSi), is introduced to the field of carbanionic polymerization. Polymerization in cyclohexane, using sec-butyllit...

Poly(phosphonate)-mediated Horner–Wadsworth–Emmons reactions

A novel, general protocol for a polymer-mediated Horner–Wadsworth–Emmons (HWE) reaction is reported. The polyvalent polymeric reagent was prepared via acyclic diene metathesis (ADMET) polymerization. Homo- and copolymers of reactive poly(phosphonate)s with molecular weights up to 40 000 g·mol−1 and molecular weight dispersities Đ < 2 were successfully synthesized. Subsequent application of these polymers in the HWE reaction to prepare a library of aromatic α,β-unsaturated ketones (chalcons) has proven to be an efficient synthetic pathway to minimize purification efforts, as the polymeric side-product can be removed by simple precipitation. In this paper we also demonstrate for the first tim…

Poly(phosphonate)s via Olefin Metathesis: Adjusting Hydrophobicity and Morphology

Olefin metathesis step-growth (acyclic diene metathesis (ADMET)) and chain-growth (ring-opening metathesis) polymerization was used to prepare linear poly(phosphonate)s with variable hydrophilicity. The first phosphonate monomer, i.e., di(undec-10-en-1-yl) methylphosphonate, for ADMET polymerization was developed, and potentially degradable and biocompatible, unsaturated poly(phosphonate)s were prepared with molecular weights up to 23 000 g mol–1 with molecular weight dispersities Đ < 2. These polymers were studied with respect to their interaction with a calcium phosphate bone substitute material from an aqueous nanoparticle dispersion that was prepared by a solvent evaporation miniemulsio…

One-Step Block Copolymer Synthesis versus Sequential Monomer Addition: A Fundamental Study Reveals That One Methyl Group Makes a Difference

Block copolymers of polyisoprene and polystyrene are key materials for polymer nanostructures as well as for several commercially established thermoplastic elastomers. In a combined experimental and kinetic Monte Carlo simulation study, the direct (i.e., statistical) living anionic copolymerization of a mixture of isoprene (I) and 4-methylstyrene (4MS) in nonpolar media was investigated on a fundamental level. In situ 1H NMR spectroscopy enabled to directly monitor gradient formation during the copolymerization and to determine the nature of the gradient. In addition, a precise comparison with the established copolymerization of isoprene and styrene (I/S) was possible. Statistical copolymer…

Anionic Polymerization of Terpene Monomers: New Options for Bio-Based Thermoplastic Elastomers

Tapered Multiblock Copolymers Based on Farnesene and Styrene: Impact of Biobased Polydiene Architectures on Material Properties

The reactivity of the biobased monomer β-farnesene in the statistical anionic copolymerization with styrene and the effect of the bottlebrush-like polyfarnesene structure on the phase separation be...