Glycidyl 4‐Functionalized‐1,2,3‐Triazole Polymers

Abstract

A series of novel polymers, glycidyl 4‐functionalized 1,2,3‐triazole polymers (functionalized GTP) were synthesized by click functionalization of glycidyl azide polymer (GAP). Quantitative functionalization of the glycidyl polymer side groups was achieved due to the high reactivity of the azide–alkyne Huisgen cycloaddition under mild conditions. The polymers were characterized by 1H NMR, 13C NMR, IR, GPC, DLS, DSC, and TGA. We confirmed that the solubility, glass transition temperature, and decomposition temperature were controllable by changing the functional group attached at 4‐position of 1,2,3‐triazole group. Functionalized GTP expands not only the application field of GAP toward non‐explosive materials, but also the variety of poly(ethylene glycol) derivatives with different side groups.

Glycidyl Triazolyl Polymers: Poly(ethylene glycol) Derivatives Functionalized by Azide–Alkyne Cycloaddition Reaction

“…The synthesis of GTP was confirmed by 1 H‐, 13 C‐NMR, IR, and SEC . All the peaks in the 1 H‐NMR spectrum were broadened because of the short relaxation time of protons in the high molecular weight polymer.…”

“…PECH was transformed to GAP by the reaction with NaN 3 in DMSO at 100 °C for 7 h. The M n of GAP was determined to be 1344, indicating that molecular weight reduction did not occur in the azidation process. To our knowledge, the molecular weight of GAP is difficult to determine because of the intermolecular association of GAP . Presumably, the real M n value of GAP could be smaller than 1344.…”

“…GTP from commercially available PECH (Merck, molecular weight: 700 000) was synthesized by us as well . PECH was transformed to GAP by the reaction with NaN 3 in DMF at 90 °C for 24 h. The work‐up process was improved.…”

“…The reaction solution needs to be deaerated by argon or nitrogen gas to prevent the oxidation of Cu(I) catalyst. Six kinds of homopolymer GTPs functionalized by various types of side groups were reported, including the benzyl group, linear, branched, and cyclic alkyl chains, the carboxyl group, and the methoxy‐tri(ethylene glycol) chain ( Figure , Polymers 15 – 20 ) . In the work‐up process, the removal of Cu catalyst was sometimes challenging.…”

“…The thermal properties of GTPs were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) . The T g values of Polymers 15 – 20 range from −42 to 111 °C, indicating the diversity of the thermal properties of GTPs (Table ).…”