MACROMERS BY CARBOCATIONIC POLYMERIZATION .10. SYNTHESIS, CHARACTERIZATION, AND POLYMERIZABILITY OF CYANOACRYLATE-CAPPED POLYISOBUTYLENES

The objectives of this research were the synthesis and characterization of the following linear and three-arm star cyanoacrylate polyisobutylenes: [GRAPHICS] and an examination of their polymerizability. The syntheses involved the Diels-Alder protection of 2-cyanoisobutyl acrylate (IB-CA) with anthracene followed by hydrolysis and conversion to the 2-cyanoacryloyl chloride. The protected cyanoacryloly chloride was then reacted with one- or two-ended linear or three-ended three-arm star -CH2OH terminated polyisobutylenes (PIB-OH, HO-PIB-OH, and [GRAPHICS] Deprotection by excess maleic anhydride yielded the target macromers. H-1-NMR and FTIR spectroscopic analyses indicated quantitative CH2 = C(CN)COO- end-capping. The solution polymerization of a PIB-CA macromer (M(n)BAR = 2380) with N,N-dimethyl-p-toluidine (DMT) at room temperature gave high molecular weight product (M(n)BAR almost-equal-to 35,000). Solution polymerization of CA-PIB-CA and [GRAPHICS] gave networks with low (9-12%) sol fractions. The bulk copolymerization of [GRAPHICS] with IB-CA also occurred readily.