Synthesis and Characterization of the Nitrogen-Rich Hyperbranched Polymers - Poly([1,2,3]-Triazole-[1,3,5]-Triazine)s

Novel hyperbranched poly([1,2,3]‐triazole‐[1,3,5]‐triazine)s (HBP TT) were synthesized by a 1,3‐dipolar cycloaddition reaction from AB2 monomer – 2‐azido‐4,6‐bis‐prop‐2‐yn‐1‐yloxy‐ [1,3,5]‐triazine (ABPOT). The monomer contains one azide group A and two terminal alkyne units B. Thermal polymerization of ABPOT in bulk or in DMF solution leads to hyperbranched polymers containing both 1,4‐ and 1,5‐disubstituted [1,2,3]‐triazoles. The monomer was also polymerized catalytically in the presence of Cu(I) salts under mild reaction conditions in DMSO solution and in bulk affording hyperbranched poly‐[1,2,3]‐triazoles 1,4‐disubstituted only. The reactions lead to the products soluble in aprotic polar solvents like DMSO or DMF. Side reactions can proceed in a few cases, particularly: (i) homocoupling of alkyne groups, leading to the formation of insoluble products as a result of cross‐linking, (ii) isomerization of propynyloxytriazine fragments to propynyl‐ or propadienyltriazinone ones, and (iii) hydrolysis of triple bonds without the loss of solubility. Heats of formation of monomer and synthesized polymers were calculated from their combustion heats. All products were characterized by NMR‐, IR‐spectroscopy, and size exclusion chromatography (SEC) data. The obtained results open the prospect for the use of HBP TT as the high‐enthalpy modifiers for energetic and non‐energetic binders.