Direct access to poly(glycidyl azide) and its copolymers through anionic (co-)polymerization of glycidyl azide

• Published in: Nature communications Vol. 10; no. 1; pp. 293 - 9
• Main Authors: Boopathi, Senthil K., Hadjichristidis, Nikos, Gnanou, Yves, Feng, Xiaoshuang
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 17.01.2019; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/455; 639/638/455/941; 639/638/455/959; Carbon dioxide; Carbon monoxide; Chemical synthesis; Copolymerization; Cyclohexene; Epichlorohydrin; Glycidyl azide polymer; Humanities and Social Sciences; Monomers; multidisciplinary; Organic chemistry; Polycarbonate resins; Polydispersity; Polyepichlorohydrins; Polyethers; Polymerization; Polymers; Propylene oxide; Ring opening polymerization; Salts; Science; Science (multidisciplinary); Solid propellants
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-018-08251-1

Glycidyl azide polymer or poly(glycidyl azide) which is considered as an excellent energetic binder or plasticizer in advanced solid propellants is generally obtained by post-modification or azidation of poly(epichlorohydrin). Here we report that glycidyl azide can be directly homopolymerized through anionic ring-opening polymerization to access poly(glycidyl azide) using onium salts as initiator and triethyl borane as activator. Molar masses of poly(glycidyl azide) up to 11.0 Kg/mol are achieved in a controlled manner with a narrow polydispersity index (PDI ≤ 1.2). Similarly, alternating poly(glycidyl azide carbonate) are also prepared through alternating copolymerization of glycidyl azide with carbon dioxide. Lastly, the copolymerization of glycidyl azide with other epoxide monomers is carried out; the azido functions carried by glycidyl azide which are successfully incorporated into the backbones of polyethers and polycarbonates based on cyclohexene oxide and propylene oxide subsequently served to introduce other functions by click chemistry. Poly(glycidyl azide) is an excellent energetic binder or plasticizer, however its production relies on post-modificaiton strategies. Here, the authors directly produced Poly(glycidyl azide) via anionic ring-opening polymerization of glycidyl azide monomer, which is additionally co-polymerized with CO 2 and epoxides.