Cyclopolymerization of amine-linked diacrylate monomers

New diacrylate monomers for cyclopolymerization were synthesized from the reaction of ethyl α-chloromethylacrylate (ECMA) and t-butyl α-bromomethyl acrylate (TBBr) with aniline, adamantyl amine, t-butyl amine, cyanamide, and 4-tetradecyl aniline in yields of ca. 50–70%. Bulk and solution polymerizations with azobisisobutyronitrile (AIBN) at 60–85°C gave soluble cyclopolymers with M_n and M_w ranging from 10,000–30,000 and 12,000–40,000, respectively. The ECMA–cyanamide derivative only gave crosslinked polymers. ¹H and ¹³C solution NMR indicated high cyclization efficiency (>93%). A prototype NLO polymer was synthesized from the reaction of the TBBr–aniline cyclopolymer with tetracyanoethylene. The p-hydroxyaniline derivative of ECMA was synthesized and used for further derivatizations; for example, the benzoate ester was made and polymerized (M_n = 21,260 and M_w = 40,317). The ester groups of the TBBrndash;aniline polymer were hydrolyzed completely to give a polymer with both acid and base moieties. DSC thermograms showed glass transitions of 132°C for the ECMA–aniline derivative, 192°C for the ECMA–adamantyl derivative, 53°C for the TBBr–tetradecylaniline derivative, and 120° for the ECMA–p-benzoylaniline derivative. The ECMA–t-butyl amine polymer showed no obvious T_g. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2111–2121, 1997