title: Formation of alternating copolymers via spontaneous copolymerization of 1,3-dehydroadamantane with electron-deficient vinyl monomers.
abstract: Copolymerizations of 1,3-dehydroadamantane, 1, and various vinyl monomers were carried out in THF at room temperature. On mixing 1 with electron-deficient vinyl monomers, such as acrylonitrile and methyl acrylate, in the absence of any initiator, the copolymerization spontaneously proceeded to give alternating copolymers in 28-88% yield. By contrast, no reaction of 1 occurred at all when isobutyl vinyl ether or styrene was mixed under similar conditions. These contrastive results indicate the high electron density of a central sigma-bond in a strained [3.3.1]propellane derivative, 1. Alternating sequences of the resulting copolymers were characterized by NMR and MALDI-TOF-MS measurements. DSC and TGA measurements revealed the high thermal stability of the alternating copolymers containing bulky, stiff, and strain-free adamantane skeletons.
authors.affiliation: Department of Organic and Polymeric Materials, Tokyo Institute of Technology, 2-12-1-H-119, Ohokayama, Meguro-ku, Tokyo 152-8552, Japan.
authors.forename: Shin-Ichi
authors.initials: S
authors.lastname: Matsuoka
authors.forename: Naoto
authors.initials: N
authors.lastname: Ogiwara
authors.forename: Takashi
authors.initials: T
authors.lastname: Ishizone