A scalable and continuous access to pure cyclic polymers enabled by quarantined heterogeneous catalysts

Cyclic polymers are topologically interesting and envisioned as a lubricant material. However, scalable synthesis of pure cyclic polymers remains elusive. The most straightforward way is to recycle a used catalyst for the synthesis of cyclic polymers. Unfortunately, it is demanding because of the catalyst’s vulnerability and inseparability from polymers, which depreciates the practicality of the process. Here, we develop a continuous process streamlined in a circular way that polymerization, polymer separation, and catalyst recovery happen in situ, to dispense a pure cyclic polymer after bulk ring-expansion metathesis polymerization of cyclopentene. It is enabled by introducing silica-supported ruthenium catalysts and a newly-designed glassware. Also, different depolymerization kinetics of the cyclic polymer from its linear analogue is discussed. This process minimizes manual labor, maximizes security of vulnerable catalysts, and guarantees purity of cyclic polymers, thereby showcasing a prototype of a scalable access to cyclic polymers with increased reusability of precious catalysts (≥415,000 turnovers).

Sliding dynamics of multi-rings on semiflexible polymer in poly[n]catenanes

The sliding dynamics of one- or multi-rings along a semiflexible cyclic polymer in radial poly[n]catenanes is investigated using molecular dynamics simulations. The fixed and fluctuating (non-fixed) semiflexible central cyclic polymers...

Investigation of the influence of impurities on the ring-opening polymerisation of L-Lactide from biogenous feedstock

In order to use a L-lactide monomer that is derived from fermentation processes it is necessary to understand, how the polymerisation process is influenced by impurities which derive from the production process. We have selected a group of likely contaminants and added them at various concentrations to the polymerisation of L-lactide using tin (II)-2-ethylhexanoate as catalyst and 2-methoxyethanol as initiator. The effect of impurities onto the global properties of the polymers such as glass transition temperature, melting point and molecular mass distribution were investigated and NMR and MALDI mass spectrometry were used to identify structural changes within the polymers. Thus, it could be shown that in reference experiments cyclic polymers and linear polymers with different starting groups are formed. Addition of ethanol and sodium carbonate showed the strongest influence on molecular masses as well as polymer structures, which could be elucidated by interpretation of the MALDI mass spectra and NMR data.