| 1. The application of 1,1′-binaphthyl-based polymers in Ziegler-Natta type polymerization of olefins was examined. The synthesis of a novel poly(BINOL) was demonstrated. These polymers were tested as supports of transition metal catalysts for olefin polymerization, and also as supports for the aluminum cocatalysts. Several polymers were active in the polymerization of ethylene, propylene, hexene, and styrene. High molecular weights were obtained in the polymerization of ethylene.; Three 1,1′-binaphthyl-based diastereomeric chiral ligands containing conformation-defined 3,3′-aryl substituents were synthesized and characterized. These compounds were isolated from the product mixture of the Suzuki coupling of (S)-3,3′-diiodo-2,2 ′-bis-methoxymethoxy-[1,1′]binaphthalenyl with 2-methoxy-1-naphthylboronic acid. The absolute structures of these compounds were determined by a single crystal X-ray analysis of the (S,S,S)-diastereomer. Among the three diastereomers, i.e., (S,S,S), (R,S,S) and (R,S,R), the (S,S,S) compound showed the highest catalytic activity as well as the highest enantioselectivity for the diethylzinc addition to aldehydes. The (S,S,S) isomer catalyzed the reaction of diethylzinc with both aromatic and aliphatic aldehydes with up to 96% ee and 90% yield. The other two isomers gave lower catalytic activity and enantioselectivity. This demonstrates that the 3,3′-aryl conformation of the 1,1′-binaphthyl ligands plays a very important role in the catalytic process. The study of these diastereomeric compounds provided new insight into the design of chiral 1,1′ -binaphthyl-based monomeric and polymeric ligands for asymmetric catalysis.; 2. The synthesis and functionalization of hyperbranched poly(carbosilane)s with hexafluoroisopropanol groups provides materials suitable for a variety of sensor applications ranging from collectors to sensors. The copolymers were made at 20 mol % intervals by hydrosilation polymerization. Alternative methods such as ring-opening polymerization gave higher molecular weight polymers. The hydrogen-bond acidic polymers provide stable materials for sorbent coatings for vapor sensing with Surface Acoustic Wave (SAW) and MEMS devices. The sensors respond reversibly to air samples containing nitroaromatics and organophosphonates. Detection of organophosphonates below 0.1 mg/m3 have been demonstrated, as well as low levels of nitroaromatic compounds. Model compounds have been synthesized to provide a better understanding of the physicochemical properties of polymers. Spectroscopic characterization and X-ray diffraction studies reveal the 6-, 4,6-, and 6,8-substitution patterns on the naphthyl groups of the model compounds. |
