It was previously reported that peroxides can be employed for crosslinking of polymers . Their main advantages as crosslinking agents are: (1) ability to crosslink saturated and unsaturated elastomers; (2) high temperature resistance; (3) good elastic behavior at higher temperature; (4) low moisture uptake; and no staining or discoloration of the resulting products. It was shown that the crosslinking was dependent on the reaction temperature, peroxide concentration, and crosslinking time . The effect of type and amount of peroxide and its decomposition rate on the crosslinking of several hydrophobic polymers was also investigated. Commercially available peroxides show relatively high hydrogen abstraction ability, which makes them good crosslinking agents for many organic polymers. Nevertheless, there are also a number of disadvantages. The decomposition products of peroxides can be volatile, exhibit a distinct smell and can lead to blooming effects. They may be extracted from the crosslinked compound by solvent, but this is clearly not a preferred approach . Finally, the safety demands during the handling and storage of peroxides are considerable. As an alternative, polymer containing peroxide moieties in their side chains are known. For this, a plethora of different peroxide containing monomers with different structure can be used for (co)polymerization. It has been suggested that 5-tert-butylperoxy-5-methyl-1-hexen-3-yne (PM) is a particularly interesting peroxide monomer due to its rather stable peroxide groups during storage and good reactivity during the polymerization . In fact, the synthesis of copolymers containing PM along with other reactive groups has been reported previously . These copolymers act as radical generators and have potential as compatibilization agents and surface modifiers. Therefore, such polymers have been studied for different applications, e.g. to interact with the interface of polymer colloidal systems, as coupling agents in polymer composites or as amphiphiles in aqueous solutions. In this, their ability to react simultaneously or sequentially by radical and condensation polymerization mechanism is of particular interest .