In the present study, acetoacetic ester-terminated polyether was selected as a modifier to prepare a new type of polyether phenolic resin, which was successfully prepared by pre-synthesis modification. It is used to prepare interpenetrating cross-linked network structure modified phenolic foam with excellent mechanical properties. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (1H NMR, 13C NMR) were used to characterize the molecular structure of the polyether phenolic resin. The results showed that the acetoacetic ester-terminated polyether successfully modified the phenolic resin and introduced a polyether skeleton into the resin structure. The effect of changing the added amount of acetoacetic ester-terminated polyether from 10% to 20% of the phenol content on the mechanical properties and microstructure of the modified phenolic foam was investigated. The results showed that when the amount of acetoacetic ester-terminated polyether was 16% the amount of phenol, this resulted in the best toughness of the modified foam, which had a bending deflection that could be increased to more than three times that of the base phenolic foam. The modified phenolic foam cell diameter was reduced by 36.3%, and the distribution was more uniform, which formed a denser network structure than that of the base phenolic foam. The bending strength was increased by 0.85 MPa, and the pulverization rate was as low as 1.3%.
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