The 1,4-nickel migration process from aryl to alkenyl groups is now reported for the first time. The alkenyl nickel intermediates generated by this highly stereoselective migration process can be coupled with brominated alkanes to form multisubst...
The Effect of the Axle End Structure and Number of Through‐Space Bonds on the Properties of Rotaxane Crosslinked Polymers
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A series of structure-definite rotaxane crosslinkers were synthesized to evaluate the mechanism for toughening a rotaxane crosslinked polymer (RCP). The size of the axle end was important for toughening RCP, and a rotaxane crosslinker worked more effectively than a rotaxane. The mobility of the crosslinking point, in terms of the rotational and flipping movements, was more crucial for toughening RCP than that of the translational movement.
A rotaxane crosslinker (RC) is known to toughen the resulting rotaxane crosslinked polymer (RCP) via a stress dispersion effect that is attributed to the movable nature of the crosslinking structure. To evaluate this toughening mechanism in detail, a series of structure-definite RCs equipped with different axle end structures or different numbers of wheel components were synthesized, and subjected to free radical polymerization with a vinyl monomer to obtain RCPs. Analyses of the obtained RCPs revealed that the size of the axle end structure should be well-balanced to produce a strong toughening effect, and a rotaxane crosslinker works more effectively than rotaxane to toughen RCPs. The mobility of the crosslinking points, in terms of rotational and flipping movements, was more crucial to toughening the RCP than that of translational movement along the axle. The first observation of the above crucial findings proved the utility of the systematic molecular design used in this study.Zum Volltext
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