Preferential screw sense, optically active chains

Another significant cooperativity effect in preferential helical screw sense optically active copolymers is the majority rule phenomenon.18bl8q In this case, the screw sense of a helical main chain with unequal proportions of opposite chirality enantiopure chiral side groups is controlled by the enantiomeric excess only. Since this phenomenon was first reported from poly-a-olefins made of vinyl co-monomers bearing nonenantiopure chiral moieties by Green et al.8b and Pino et al.,16b this majority rule has been established in... 

Olefin Polymers Isotactic polymers of propylene and 1-butene obtained by optically active metallocene catalyst (145) have been reported to show large specific rotation in suspension ([a]D-123°, -250° for polypropylene [a]D+130° for polybutene), which was lost when the polymers were completely dissolved or heated [176,177]. The optical activity was ascribed to a helical conformation of the polymer chain with preferential screw sense. 

For example, the sergeants and soldiers experiment features a preferential screw-sense helical amplification in optical active copolymers with racemic helical structures named by Green et al. [17,18], This effect means that a small portion of enantiopure chiral side groups determines the overall screw sense (P or M) of the helical main chain bearing a majority of achiral side groups, and a population of helicity with one preferential screw-sense is nonlinearly amplified as a function of the chiral impurity. Since the first report of this phenomenon in poly-a-olefin copolymers by Pino et al. [21],... 

Helix-sense-selective polymerization is the reaction that yields polymers with a helical conformation with excess screw sense. Right- and left-handed helices are mirror images (atropisom-ers), and if one of the two is preferentially synthesized for a polymer chain, the polymer can be optically active (1-9]. 

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