Thermal decomposition of poly(tert‐butyl N‐vinylcarbamate)

Abstract

synopsisPyrolysis of poly(tort-butyl N-vinylcarbamate) at 18,52OO0C in bulk yields a rigid foam containing cyclic urea units, primary amine units, and a small amount of urea crosslinks. The yield of primary amine units (ca. 13%) and the yields of carbon dioxide (ca. 579r,), isobutylene (ca. 57%), and brf-butanol formed in this reaction indicate that it involves pairwise decomposition of adjacent carbamate units to form cyclic urea units, tert-butanol, carbon dioxide, and isobutylene. The vinyl amine units are formed from carbamate units that become flanked by urea units. The amounts of amine units and residual carbamate units were determined as a function of degree of pyrolysis by an ion-exchange technique and agreed with valuev expected for a random cyclization process. The pyrolyzed polymers are useful as ion-exchange resins and as rigid foams having good thermal stability.

An electrochemical Hofmann rearrangement on acrylamide copolymers

“…These preliminary results allude to the potential of this chemistry as a platform to synthesise and characterise alkyl/aryl-Nvinyl carbamate functionalised (co)polymers which are synthetically challenging by other routes and as a result have received limited attention in the field up to now. 45,46 Alternative nucleophilic reacting partners including amines and thiols are also being explored as potential routes to urea and carbamothioate functionalised (co)polymers respectively. Furthermore, by exploiting the control enabled by reversible deactivation radical polymerization (RDRP), the potential of incorporating these functional groups into more complex (co) polymer compositions and architectures is also being investigated.…”