Polycarbosilanes are flexible metal-containing polymers with high thermal and chemical stability. We consider that polycarbosilanes can be key polymers to develop new functional materials. Silacyclobutanes are known as good monomers to prepare polycarbosilanes by various ring-opening polymerizations.Here, we synthesized a silacyclobutane having an epoxy functional group, 1-(3,4-epoxybutyl)-1-methylsilacyclobutane (OBMSB), and examined its transition-metal-catalyzed ring-opening polymerization. As a result, we found that a polysilacyclobutane having an epoxy pendant group (polyOBMSB) was obtained by heating the monomer in toluene at 70 oC for 1 h in the presence of platinum vinyldimethyldisiloxane catalyst (Figure 1). Ring-opening polymerization of the four-membered silacarbocycle proceeded with keeping the epoxy ring without side reactions in this condition. Copolymerization of OBMSB and 1,1-diethylsilacyclobutane (DESB) also proceeded in the same polymerizatio condition (Figure 2).The obtained polyOBMSB homopolymer and poly(DESB-co-OBMSB) copolymers could be transformed to networked polymers through post crosslinking of the epoxy groups by heating the polymer at 80 oC for 2 h in the presence of catalytic amount of benzylmethylnaphthylsulfonium hexafluoroantimonate (SI-60), a thermally latent cationic polymerization initiator.

Polymerization of silacyclobutane having an epoxy functional group and its application to networked polymer system

248th National Meeting (2014)

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