Cyclopolymerization of amine-linked diacrylate monomers

✍ Scribed by Duygu Avci; Camille Haynes; Lon J. Mathias

• Book ID: 101270190
• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 233 KB
• Volume: 35
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19970730)35:10<2111::aid-pola26>3.0.co;2-i

✦ Synopsis

New diacrylate monomers for cyclopolymerization were synthesized from the reaction of ethyl a-chloromethylacrylate (ECMA) and t-butyl a-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 60-85ЊC 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. 1 H and 13 C solution NMR indicated high cyclization efficiency (ú93%). 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 Å 21,260 and M w Å 40,317). The ester groups of the TBBr-aniline polymer were hydrolyzed completely to give a polymer with both acid and base moieties. DSC thermograms showed glass transitions of 132ЊC for the ECMA-aniline derivative, 192ЊC for the ECMA-adamantyl derivative, 53ЊC for the TBBr-tetradecylaniline derivative, and 120Њ for the ECMA-p-benzoylaniline derivative. The ECMA-t-butyl amine polymer showed no obvious T g .