The objective of this study is to develop a fast curing phenolic formaldehyde (PF) and polymeric diphenyl methane isocyanate (MDI) based hybrid resin system for wood products applications. Various formulas of PF resins were synthesized with different formaldehyde to phenol ratio, sodium hydroxide to phenol and isocyanate group (-NCO) to hydroxyl group (-OH) molar ratios. The shear bonding strength property was used to evaluate and optimize the formulations by appropriate sample preparation. The optimized resins were characterized by rheometer, Fourier transform infrared spectroscopy (FTIR) and other methods. In order to eliminate the influence of hydroxyl groups from water in the PF resin, a frozen dried method was applied to remove the water while keeping PF resin in liquid state. Acetone was used to disperse the hybrid co-polymer to improve the mobility of the mixture of frozen dried PF resins and MDI. An unexpected phenomenon was observed when the two resins were mixed in acetone and a sharp reaction occurred. This led to an assumption that acetone promoted the curing of hybrid resin. The effect of acetone on the curing behavior of hybrid resin was studied by differential scanning calorimetry (DSC), confocal laser scanning microscope (CLSM) and other techniques. It was confirmed that acetone promoted the curing of the co-polymer system. The gel time of hybrid resin with acetone decreases sharply compared to that of pure phenolic resin and original hybrid resin. Acetone also helped the hybrid resin to have better penetration behavior by improving the mobility and this also resulted in less variation of the strength distribution. Finally, lap shear samples were prepared at room temperature curing commercial polyurethane (PU), phenol-resorcinolormaldehyde resin (PRF) and laboratory made hybrid resins based on PF and MDI to compare the shear strength of different resins under different application conditions. The strength reduction of frozen dried PF with acetone/MDI is the lowest in humidity, temperature and humidity-temperature conditions. With just humidity condition, its shear strength reduction is significantly lower than that of any other resins including the solid wood control.

Urea formaldehyde (UF) resins are widely used as adhesives for wood-based composites. These thermosetting polymers have advantages of relative low price, fast curing speed, and relative good bonding performance. However, UF resin bonded composites are designed for interior applications due to its weak water resistance. Moreover, traditional prevalent ways for recycling wood-based composites face problems caused by UF resins. In this project, the reuse of cured UF resins was systematically studied. The verification and characterization of crystalline structures in cured UF resins were conducted. The results showed that the crystalline regions were accounted for nearly 14.48% in a typical 1.2 formaldehyde to urea (F/U) molar ratio UF resin. The details of the resin crystalline regions, such as grain sizes and interplanar spacing (d-spacing), were characterized. The crystalline structures, nevertheless, did not affect the UF resin hydrothermal hydrolysis in this study. The reuse of cured UF resin was started with a hydrothermal hydrolysis. Under 140 °C and 2 h of hydrothermal process, 20 mL of 30 w.t. % formaldehyde water solution was able to depolymerize up to 1.7 g of cured UF resin. The hydrolyzed formaldehyde solutions were directly used as normal formaldehyde solutions for UF resin synthesis. The synthesized resin (named as UUF resin) contained about 6 w.t. % of cured UF resin and presented similar chemical structures and bonding performance as normal UF resins. Hybrid resins made of UUF resin and polymeric 4-4 diphenyl methane diisocyanate (pMDI) were prepared. The pMDI was found evenly dispersed in the hybrid resins by using acetone as its solvent. These hybrid resins resulted in faster curing and stronger bonding performance than pure UUF resins. Furthermore, the hybrid resin was used in a new bonding design, which used southern pine wood radial section features. This design generated finger joint like bonding interfaces by hot pressing two resin coated wood radial sections. The bonding strength and bond line stability were enhanced by this design.