Mechanical Activation of Chemical Bonds at Polymer Interfaces

Polymer brushes are a specific class of polymer thin films in which each chain is tethered to the underlying substrate via one chain end. In sufficiently densely grafted assemblies, the individual polymer chains are forced into an extended chain conformation and form a brush-like structure, colloquially referred to as polymer brush. Upon incubation in a good solvent, polymer brushes experience swelling which leads to a tension at the polymer brush - substrate interface. This tension is believed to mechanically facilitate cleaving reactions at the tethering point resulting in the detachment of polymer chains, a process which is known as degrafting. Degrafting, and in the case of crosslinked polymer brushes delamination, has been reported for a large variety of polymer brushes and surface materials. Even though this phenomenon is already known for more than two decades, in depth understanding of the underlying mechanism is lacking and quantitative description of the process is rare. This thesis aims to gain further understanding of the phenomenon by quantitative description of the degrafting process. Further, swelling induced mechanical activation at the tethering point of the polymer to the underlying substrate is discussed in the context of polymer mechanochemistry and presented as a tool to selectively facilitate mechanophore cleavage at the interface.

Chapter 1 provides a short historical review on the development of polymer mechanochemistry and gives an overview of commonly applied techniques in the field. The concept of polymer mechanochemistry is then extended to polymer brushes and the discussion results in a number of issues and research questions which are addressed in the subsequent chapters.

The preparation and characterization of polymer brushes is not trivial. In Chapter 2 limitations and challenges with focus on experimental reproducibility and thin film characterization are discussed. Chapter 3 discusses the influence of a number of factors, i.e. grafting density and molecular weight of the polymer brush, solvent quality and salt concentration in the incubation medium, on the degrafting process of hydrophilic brushes in aqueous media. Further, the degrafting behavior of polymer brushes prepared from different monomers is compared. It is attempted to correlate degrafting behavior with polymer brush swelling.

Contradicting results concerning the actual cleaving point of chains in polymer brushes are found in literature. In Chapter 4 presents structures incorporating only one single potential cleaving point. However, non-specific degrafting could not completely be suppressed. Further, a disulfide bond and oxy-norbornene moiety, commonly used mechanophores, were introduced at the anchoring point.

In Chapter 5 the limitation of unwanted background hydrolysis was circumvented by investigating degrafting processes in dry organic media. Specific cleavage of the two mechanophores, disulfide and oxy-norbornene, could be demonstrated.