Facile, Efficient, and Safe Copper‐Free Synthesis of Glycidyl Triazolyl Polymers

ABSTRACT In this study, a new synthetic procxe was proposed to solve the problems in the conventional copper‐free glycidyl triazolyl polymer (GTP) synthesis: (1) the explosion risk of the solid glycidyl azide polymer (GAP) and (2) large material loss of the electron‐deficient alkyne derivative. In order to demonstrate the superiority of the new synthetic procedure, five kinds of GTPs were synthesized with different types of alkyne derivatives. GAP was synthesized through the reaction between polyepichlorohydrin and sodium azide in N , N ‐dimethylformamide. For handling impact‐ and friction‐sensitive solid GAP safely, it was purified through liquid–liquid extraction and stored as a stock solution without isolating it in the solid state. Through the new procedure utilizing a stock solution, the reaction efficiency in GTP synthesis was greatly improved, which resulted in reducing material loss (Feed ratio alkyne/azide: from 4.0 to 1.3) and reaction time (from 72 to 24 h). Thanks to the facile, efficient, and safe synthetic method, enough amounts of GTP samples could be prepared for characterizing not only physicochemical properties (density, molecular weight, glass transition temperature, thermal decomposition temperature, surface free energy) but also mechanical properties (Young's modulus, fracture stress and strain). The synthetic procedure reported herein will accelerate the research and development of functional GTPs with tunable physical properties.