Search Results (4)

The production of CO₂-containing polymers is still very demanding in terms of controlling the synthesis of products with pre-defined CO₂ content and molecular weight. An elegant way of synthesising these polymers is via CO₂-containing building blocks, such as cyclic ethylene carbonate (cEC), via catalytic ring-opening polymerisation. However, to date, the mechanism of this reaction and control parameters have not been elucidated. In this work, using DFT-metadynamics simulations for exploiting the potential of the polymerisation process, we aim to shed more light on the mechanisms of the interaction between catalysts (in particular, the catalysts K₃VO₄, K₃PO₄, and Na₂SnO₃) and the cEC monomer in the propagation step of the polymeric chain and the occurring CO₂ release. Confirming the simulation results via subsequent kinetics measurements indicates that, depending on the catalyst’s characteristics, it can be attached reversibly to the polymeric chain during polymerisation, resulting in a defined lifetime of the activated polymer chain. The second anionic oxygen of the catalyst can promote the catalyst’s transfer to another electrophilic cEC monomer, terminating the growth of the first chain and initiating the propagation of the new polymer chain. This transfer reaction is an essential step in controlling the molecular weight of the products. Full article

Block copolymers synthesized via Atom Transfer Radical Polymerization from alkyl acrylate and t-butyl acrylate and the subsequent hydrolysis of the t-butyl acrylate to acrylic acid were systematically varied with respect to their hydrophobic part by the variation in the alkyl chain length and the degree of polymerisation in this block. Depending on the architecture of the hydrophobic part, they had a more or less pronounced tendency to form copolymer micelles in an aqueous solution. They were employed for the preparation of IPECs by mixing the copolymer aggregates with the polycations polydiallyldimethylammonium chloride (PDADMAC) or q-chit. The IPEC structure as a function of the composition was investigated by Static Light and Small Angle Neutron Scattering. For weakly-associated block copolymers (short alkyl chain), complexation with polycation led to the formation of globular complexes, while already existing micelles (long alkyl chain) grew further in mass. In general, aggregates became larger upon the addition of further polycation, but this growth was much more pronounced for PDADMAC compared to q-chit, thereby leading to the formation of clusters of aggregates. Accordingly, the structure of such IPECs with a hydrophobic block depended largely on the type of complexing polyelectrolyte, which allowed for controlling the structural organisation via the molecular architecture of the two oppositely charged polyelectrolytes. Full article

Risks from rockfall and land sliding can be controlled by high-tensile steel nets and meshes which stabilise critical areas. In many cases, a recultivation of the land is also desired. However, high-tensile steel meshes alone are not always sufficient, depending on the location and the inclination of the stabilised slope, to achieve rapid greening. Cellulose fibres exhibit high water binding capacity which supports plant growth. In this work, a hybrid structure consisting of a nonwoven cellulose fibre web and a steel mesh was produced and tested under outdoor conditions over a period of 61 weeks. The cellulose fibres are intended to support plant growth and soil fixation, and thus the biodegradation of the structure is highly relevant, as these fibres will become part of the soil and must be biodegradable. The biodegradation of the cellulose fibres over the period of outdoor testing was monitored by microscopy and analytical methods. The enzymatic degradation of the cellulose fibres led to a reduction in the average degree of polymerisation and also a reduction in the moisture content, as polymer chain hydrolysis occurs more rapidly in the amorphous regions of the fibres. FTIR analysis and determination of carboxylic group content did not indicate substantial changes in the remaining parts of the cellulose fibre. Plant growth covered geotextiles almost completely during the period of testing, which demonstrated their good compatibility with the greening process. Over the total period of 61 weeks, the residual parts of the biodegradable cellulose web merged with the soil beneath and growing plants. This indicates the potential of such hybrid concepts to contribute a positive effect in greening barren and stony land, in addition to the stabilising function of the steel net. Full article

Poly(phosphazenes)(PZ) are versatile polymers due to their tunable properties that can be tailored for specific applications. Despite extensive experimental research, not all properties are tested, and the list of PZs studied via molecular simulations is limited. Further, a general procedure to generate and test PZ systems is lacking. We present an in situ polymerization procedure developed to make, test, and tune the thermo-mechanical properties of four PZs—poly(dichlorophosphazene)(PZ-DC), poly[bis(2,2,2-trifluoroethoxy)]phosphazene (PZ-TFE), poly(2,2,2-trifluoroethoxy-5,6-diazidohexanoxy) phosphazene (PZ-Azido), and poly(2,2,2-trifluoroethoxy-5,6-dinitratohexanoxy)phosphazene (PZ-Nitrato) via molecular dynamics simulations. The predicted thermo-mechanical properties (i.e., density and glass transition temperature) agreed with experimental values when a direct comparison of PZ systems was possible. This demonstrates the reproducibility and reliability of our procedure which will help understand the behaviour of PZs at the molecular scale. Full article