CYCLOPOLYMERIZATION OF AMINE-LINKED DIACRYLATE MONOMERS

New diacrylate monomers for cyclopolymerization were synthesized from the reaction of ethyl alpha-chloromethylacrylate (ECMA) and t-butyl al pha-bromomethyl acrylate (TBBr) with aniline, adamantyl amine, t-butyl amine, cyanamide, and 4-tetradecyl aniline in yields of ca. 50-70%. B ulk and solution polymerizations with azobisisobutyronitrile (AIBN) at 60-85 degrees C gave soluble cyclopolymers with M-n and M-w ranging f rom 10,000-30,000 and 12,000-40,000, respectively. The ECMA-cyanamide derivative only gave crosslinked polymers. H-1 and C-13 solution NMR i ndicated high cyclization efficiency (>93%). A prototype NLO polymer w as synthesized from the reaction of the TBBr-aniline cyclopolymer with tetracyanoethylene. The p-hydroxyaniline derivative of ECMA was synth esized and used for further derivatizations; for example, the benzoate ester was made and polymerized (M-n = 21,260 and M-w = 40,317). The e ster groups of the TBBr-aniline polymer were hydrolyzed completely to give a polymer with both acid and base moieties. DSC thermograms showe d glass transitions of 132 degrees C for the ECMA-aniline derivative, 192 degrees C for the ECMA-adamantyl derivative, 53 degrees C for the TBBr-tetradecylaniline derivative, and 120 degrees for the ECMA-p-benz oylaniline derivative. The ECMA-t-butyl amine polymer showed no obviou s T-g. (C) 1997 John Wiley & Sons, Inc.