Design, Synthesis and Characterization of Vitrimers with Low Topology Freezing Transition Temperature.

Vitrimers are crosslinked polymeric materials that behave like fluids when heated, regulated by the kinetics of internal covalent bond-exchange that occurs rapidly at or above the topology freezing transition temperature (Tv) of the vitrimer, making these materials readily reprocessable and recyclable. We report two novel multiphase vitrimeric materials prepared by the cross-linking of two polymers, namely poly(triethylene glycol sebacate) and poly(2-hydroxyethyl acrylate), using zinc acetate or tin(II) 2-ethylhexanoate as catalysts, which exhibit significantly low Tv temperatures of 39 °C and 29 °C, respectively. The transesterification reactions allow rapid and pronounced stress relaxation at high temperatures, following the Arrhenius law. The lower Tv of these vitrimers could be attributable to the flexible long chains of these polymers and the significant excess of OH moieties present along the main chain of the polymer. The design of such multiphase vitrimers is not only useful for the practical application of vitrimers to reduce plastic waste but could also facilitate further development of functional polymer materials that can be reprocessed at low temperatures.

Binding of amphiphilic and triphilic block copolymers to lipid model membranes: the role of perfluorinated moieties.

A novel class of symmetric amphi- and triphilic (hydrophilic, lipophilic, fluorophilic) block copolymers has been investigated with respect to their interactions with lipid membranes. The amphiphilic triblock copolymer has the structure PGMA(20)-PPO(34)-PGMA(20) (GP) and it becomes triphilic after attaching perfluoroalkyl moieties (F9) to either end which leads to F(9)-PGMA(20)-PPO(34)-PGMA(20)-F(9) (F-GP). The hydrophobic poly(propylene oxide) (PPO) block is sufficiently long to span a lipid bilayer. The poly(glycerol monomethacrylate) (PGMA) blocks have a high propensity for hydrogen bonding. The hydrophobic and lipophobic perfluoroalkyl moieties have the tendency to phase segregate in aqueous as well as in hydrocarbon environments. We performed differential scanning calorimetry (DSC) measurements on polymer bound lipid vesicles under systematic variation of the bilayer thickness, the nature of the lipid headgroup, and the polymer concentration. The vesicles were composed of phosphatidylcholines (DMPC, DPPC, DAPC, DSPC) or phosphatidylethanolamines (DMPE, DPPE, POPE). We showed that GP as well as F-GP binding have membrane stabilizing and destabilizing components. PPO and F9 blocks insert into the hydrophobic part of the membrane concomitantly with PGMA block adsorption to the lipid headgroup layer. The F9 chains act as additional membrane anchors. The insertion of the PPO blocks of both GP and F-GP could be proven by 2D-NOESY NMR spectroscopy. By fluorescence microscopy we show that F-GP binding increases the porosity of POPC giant unilamellar vesicles (GUVs), allowing the influx of water soluble dyes as well as the translocation of the complete triphilic polymer and its accumulation at the GUV surface. These results open a new route for the rational design of membrane systems with specific properties.