Bio-oil was added as a substitute for phenol for the preparation of a foaming phenolic resin (PR), which aimed to reduce the brittleness and pulverization of phenolic foam (PF). The components of bio-oil, the chemical structure of bio-oil phenolic resin (BPR), and the mechanical performances, and the morphological and thermal properties of bio-oil phenolic foam (BPF) were investigated. The bio-oil contained a number of phenols and abundant substances with long-chain alkanes. The peaks of OH groups, CH₂ groups, C=O groups, and aromatic skeletal vibration on the Fourier transform infrared (FT-IR) spectrum became wider and sharper after adding bio-oil. These suggested that the bio-oil could partially replace phenol to prepare resin and had great potential for toughening resin. When the substitute rate of bio-oil to phenol (B/P substitute rate) was between 10% and 20%, the cell sizes of BPFs were smaller and more uniform than those of PF. The compressive strength and flexural strength of BPFs with a 10–20% B/P substitute rate increased by 10.5–47.4% and 25.0–50.5% respectively, and their pulverization ratios decreased by 14.5–38.6% in comparison to PF. All BPFs maintained good flame-retardant properties, thermal stability, and thermal isolation, although the limited oxygen index (LOI) and residual masses by thermogravimetric (TG) analysis of BPFs were lower and the thermal conducticity was slightly greater than those of PF. This indicated that the bio-oil could be used as a renewable toughening agent for PF.

The aging properties of phenol-formaldehyde resin modified by bio-oil (BPF) were analyzed using ultraviolet (UV) weathering. The variations on bonding strength of BPF were measured, and the changes on microstructure, atomic composition and chemical structure of BPF were characterized by using a scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR), respectively. With the increase of aging time, the bonding strength decreased gradually, the resin surface became rougher and the O/C radio of resin surface increased. However, the loss rate of bonding strength of BPFs was 9.6–23.0% lower than that of phenol-formaldehyde resin (PF) after aging 960 h. The aging degree of BPF surfaces was smaller in comparison to PF at the same aging time. These results showed that the bio-oil had a positive effect on the anti-aging property. Analytical results revealed that with increasing the aging time, the XPS peak area of C–C/C–H decreased, while that of C=O and O–C=O increased. The intensity of methylene and ether bridges in NMR analysis decreased along with increasing the intensity of aldehydes, ketones, acids and esters. These results indicated that the aging mechanism of BPF was a process of the breakage of molecular chains and formation of oxygen-containing compounds.

Introducing bio-oil into phenolic foam (PF) can effectively improve the toughness of PF, but its flame retardant performance will be adversely affected and show a decrease. To offset the decrease in flame retardant performance, montmorillonite (MMT) can be added as a promising alternative to enhance the flame resistance of foams. The present work reported the effects of MMT on the chemical structure, morphological property, mechanical performance, flame resistance, and thermal stability of bio-oil phenolic foam (BPF). The Fourier transform infrared spectroscopy (FT-IR) result showed that the –OH group peaks shifted to a lower frequency after adding MMT, indicating strong hydrogen bonding between MMT and bio-oil phenolic resin (BPR) molecular chains. Additionally, when a small content of MMT (2–4 wt %) was added in the foamed composites, the microcellular structures of bio-oil phenolic foam modified by MMT (MBPFs) were more uniform and compact than that of BPF. As a result, the best performance of MBPF was obtained with the addition of 4 wt % MMT, where compressive strength and limited oxygen index (LOI) increased by 31.0% and 33.2%, respectively, and the pulverization ratio decreased by 40.6% in comparison to BPF. These tests proved that MMT can blend well with bio-oil to effectively improve the flame resistance of PF while enhancing toughness.

The bio-oil phenol-formaldehyde (BPF) resin, prepared by using bio-oil as a substitute for phenol, has similar bonding strength but lower price to phenol-formaldehyde (PF) resin. As a common adhesive for outdoor wood, the aging performance of BPF resin is particularly important. The variations in mass, bonding strength, microstructure, atomic composition, and chemical structure of BPF resin under five aging conditions (heat treatment, water immersion, UV exposure, hydrothermal treatment, and weatherometer treatment) were characterized by scanning electron microscope, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, respectively. Compared under five aging conditions, after aging 960 h, the mass loss of plywood and film was largest under hydrothermal treatment; the bonding strength of plywood, the surface roughness, and O/C ratio of the resin film changed most obviously under weatherometer treatment. FT-IR analysis showed that the decreased degree of peak intensity on CH₂ and C–O–C characteristic peaks of BPF resin were weaker under water immersion, hydrothermal treatment, and weatherometer treatment than those of PF resin. The comparison of data between BPF and PF resins after aging 960 h showed that adding bio-oil could obviously weaken the aging effect of water but slightly enhance that of heat. The results could provide a basis for the aging resistance modification of BPF resin.