Synthesis of model polycyclohexylene/polyethylene miktoarm star copolymers with three and four arms

The synthesis of well‐defined 3‐ and 4‐miktoarm star copolymers of the A 2 B and A 3 B types is described, where A is 1,4‐polybutadiene and B is poly(1,3‐cyclohexadiene). The synthetic approach involves the reaction of poly(1,3‐cyclohexadienyl)lithium with an excess of methyltrichlorosilane or tetrachlorosilane followed, after the removal of excess silane, by a small excess of polybutadienyllithium. Characterization was carried out by size exclusion chromatography, low‐angle laser light scattering, laser differential refractometry, and NMR spectroscopy. The complete heterogeneous catalytic hydrogenation of the A 2 B and A 3 B miktoarm stars, with a calcium carbonate‐supported palladium catalyst, leads to the formation of A 2 B and A 3 B miktoarm stars with one amorphous polycyclohexylene arm with an extremely high glass‐transition temperature and two or three crystalline polyethylene arms. Differential scanning calorimetry was used to determine the glass‐transition temperature of the amorphous blocks of the starting and hydrogenated stars and the melting temperature of polyethylene. Solid‐state 13 C NMR spectroscopy was performed to ensure the complete saturation of the polycyclohexadiene and polybutadiene arms.