Kinetic Study of the Polyaddition of Azide-Alkyne AB₂ Monomers in Nonisotermic Conditions

Abstract

Nowadays, hyperbranched polymers (HBP) are obtained by different polycondensation and polyaddition reactions [1]. Almost interest is the reaction of 1,3-dipolar cycloaddition of azides to alkynes (1,3-DCA) [2, 3]. There is a series of papers dedicated to the preparation of triazine-triazole HBPs [4, 5, 6]. These polymers were obtained by the reaction of azido-acetylene AB2 monomers polyaddition: 2-azido-4,6-bis (propyne-2-yloxy) -1,3,5-triazine (ABPOT) and 2,4-diazido-6- (propine-2-yloxy) -1,3,5-triazine (DAPOT) (Fig. 1).

Probing kinetic and mechanistic features of bulk azide–alkyne cycloaddition

“…Similar values of the activation energy are reported for bulk azide-alkyne polyaddition reaction. 36,38 The applicability of the nth-order reaction model to the measured rate data is confirmed by fitting of the integral form of this model (eqn ( 12)) to the g(a) data determined experimentally by eqn (5).…”

“…Similar values of the activation energy are reported for bulk azide–alkyne polyaddition reaction. 36,38…”

“…This model (or its special case -second-order reaction) most frequently encountered in the literature devoted to the kinetic studies of AAC, in both solution 2,34,35 and bulk. 5,[36][37][38] Also, the kinetics of AAC is described by a single rate constant, 2,5,[34][35][36][37][38] i.e. the presence of the two isomeric products is not taken into account.…”

Synthesis, Antibacterial Activity, and Cytotoxicity of Azido-Propargyloxy 1,3,5-Triazine Derivatives and Hyperbranched Polymers

“…Previously, we demonstrated the synthesis of triazine-triazole HBPs in bulk using a simple thermal azide-alkyne cycloaddition of 1,3,5-triazine monomers of the AB 2 type [21,22]. Despite the convenience and simplicity of obtaining HBPs via the polycycloaddition of AB 2 -type monomers, it is necessary to develop effective methods for the preparation of monomers that are stable during synthesis and storage.…”

Kinetics of Polycycloaddition of Flexible α-Azide-ω-Alkynes Having Different Spacer Length

“…The A-B strategy was implemented for both rigid (aromatic) and flexible (aliphatic) monomers containing reacting groups on the opposite sides of the monomer molecule (so called, α-azide-ω-alkynes) [ 10 , 12 , 13 ]. The polymerization of the flexible α-azide-ω-alkynes is more complex compared to that of the rigid ones because conformational lability of the former permits both inter- and intramolecular reactions [ 10 ].…”