The synthesis of isocyanurate-free, linear poly­(oxazolidin-2-one)­s starting from diepoxides and aromatic as well as aliphatic diisocyanates is reported. N-Heterocyclic carbenes (NHCs), liberated in situ from thermally labile CO2 adducts, in combination with Lewis acids of the simplest kind (metal halides such as LiCl and MgCl2) were employed in a cooperative manner to prepare linear polymers with molecular weights (M n) ranging from 6 to 50 kg/mol. Crucially, it is demonstrated that action of either NHC (Lewis base) or metal halide (Lewis acid) alone entails the formation of significant amounts of trimerized isocyanates (isocyanurate) and concomitant gelling of the thus cross-linked material, highlighting the advantages of a cooperative, dual catalytic approach. Reactions were conducted at 200 °C with low NHC loadings (0.5 mol %) to deliver isolated yields of 60–90% within 3–8 h polymerization time. Investigations regarding regioselectivity revealed that exclusively 5-substituted oxazolidin-2-one was formed. Notably, these transformations can be catalyzed by a combination of 1,3-dimethyl­imidazolium-2-carboxylate, a readily accessible and robust NHC-precursor tolerant toward atmospheric conditions, and well-available LiCl. A mechanism is proposed whereby the high molecular weights and the selectivity for oxazolidinone formation over side reactions are attributed to the high nucleophilicity of the NHC, cooperative monomer activation by the metal halide, and specifically chosen reaction conditions.

The manufacturing of high-performance carbon fibers (CFs) from low-cost textile grade poly(acrylonitrile) (PAN) homo-and copolymers using continuous electron beam (EB) irradiation, stabilization, and carbonization on a kilogram scale is reported. The resulting CFs have tensile strengths of up to 3.1 ± 0.6 GPa and Young's moduli of up to 212 ± 9 GPa, exceeding standard grade CFs such as Toray T300. Additionally, the Weibull strength and modulus, the microstructure, and the morphology of these CFs are determined.

We report on the pilot scale synthesis and melt spinning of poly(ethylene furanoate) (PEF), a promising bio-based fiber polymer that can heave mechanical properties in the range of commercial poly(ethylene terephthalate) (PET) fibers. Catalyst optimization and solid state polycondensation (SSP) allowed for intrinsic viscosities of PEF of up to 0.85 dLꞏg−1. Melt-spun multifilament yarns reached a tensile strength of up to 65 cN.tex−1 with an elongation of 6% and a modulus of 1370 cN.tex−1. The crystallization behavior of PEF was investigated by differential scanning calorimetry (DSC) and XRD after each process step, i.e., after polymerization, SSP, melt spinning, drawing, and recycling. After SSP, the previously amorphous polymer showed a crystallinity of 47%, which was in accordance with literature. The corresponding XRD diffractograms showed signals attributable to α-PEF. Additional, clearly assignable signals at 2θ > 30° are discussed. A completely amorphous structure was observed by XRD for as-spun yarns, while a crystalline phase was detected on drawn yarns; however, it was less pronounced than for the granules and independent of the winding speed.

Electrical resistance of the elastomeric material polychloroprene filled with multiwalled carbon nanotubes (CNTs) dispersed by using an imidazolium based ionic liquid has been measured experimentally and calculated theoretically, as a function of the applied compression/decompression force F. Both experimental and theoretical results show that the electrical resistance R of the composite exhibits non-monotonic dependence on F. This observed non-monotonic dependence R(F) is explained by different mechanisms of conductivity that are specific to the respective domains of the magnitude of the compression/decompression force F. At small F, the observed decrease of conductivity with increasing F is found to be caused by the change of an average contact distance between CNTs. At higher F, the observed increase of R with increasing F is caused by the dependence of the per-particle surface area on F. The experimentally observed dependence R(F) is adequately described by the developed theory that relies on establishing the exact relation between the CNT network structure and the electrical response of the composite. Theoretical dependence between the conductivity of the composite and the applied stress is obtained using the percolation model of the electrical conductivity of CNT network that shows excellent quantitative agreement with the experimental results.