A divergent hydrosilation/Grignard-reaction sequence, followed by hydroboration of the allyl end groups was employed to prepare a series of novel dendritic carbosilane polyols. Dendrimers with 4, 12, 36, and 108 hydroxyl end groups have been prepared. The hydroboration reactions were monitored by -NMR and MALDI-TOF and were quantitative in all cases. Using MALDI-TOF, the carbosilane dendrimers as well as the novel dendritic polyols have been characterized directly with respect to polydispersity. Whereas G2-OH consisted of mainly two species, the desired 36-ol (80%) and the 34-ol, G3-OH consisted of polyols with 92-108 hydroxyl groups. The dendritic polyols possess low glass transition temperatures (233-241 K) and thus constitute flexible polyols without polar interactions between the dendrons. The molecules appear suitable as chemically stable, flexible molecular scaffolds for the construction of unusual supermolecular architectures.

Polymerization and phase behaviour of a branched liquid crystalline bismethacrylate in a ferroelectric liquid crystal (FLC) were characterized. Addition of the monomer increases the temperature range of the smectic A phase, and, at relatively low concentrations of monomer, the temperature range increases to more than 10 times that observed in the neat FLC. Other phases such as the smectic C* phase are no longer exhibited as the monomer interferes with the inherent tilt of the FLC molecules. After polymerization, the polymer network phase separates and the phase transition temperatures return to values close to those of the FLC. The monomer also shows a high degree of orientational order before polymerization, which is retained to a large extent after polymerization. The order in the polymer network results in considerable birefringence at temperatures well above the clearing point of the pure FLC. This behaviour is induced by the order of the polymer network and interactions of the FLC molecules with the network which prevent a fraction of the FLC molecules from exhibiting typical phase behaviour. In the formation of the branched liquid crystalline bismethacrylates /FLC composites, a steady increase is observed in the polymerization rate as the polymerization temperature increases and the order of the FLC phase decreases, a behaviour signi® cantly di erent from that observed in other monomer/FLC mixtures for which the polymerization rate increases as the order of the FLC phase increases. Additionally, at appropriate polymerization temperatures around the clearing point, polymerization driven endothermic phase transitions may be observed.

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