In this study, a series of polyoxymethylene copolymers are synthesized by bulk cationic ring-opening polymerization by 1,3,5-trioxane (TOX) with 1,3-dioxolane (DOX), octamethylcyclotetrasiloxane (D4), and cyclohexane oxide (CHO) as the second monomer using phosphotungstic acid (PTA) as an initiator. The polymer products were characterized by hydrogen nuclear magnetic resonance (1H-NMR), infrared spectroscopy (IR), thermogravimetry (TG), and differential scanning calorimetry (DSC). And the copolymerization energy barrier was calculated at the b3lyp/6-31g(d) calculation level using density functional theory (DFT) to explore the copolymerization ability of the second monomer with 1,3,5-trioxane. The results showed that CHO as the second monomer more easily participated in the copolymerization reaction, and the copolymers showed better thermal stability.
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