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The complexation reaction between borate ions and phenol-formaldehyde resol resin in aqueous solution was studied by pH measurement, small model molecules and infrared spectroscopy.The results show that the complexation can proceed completely and rapidly at room temperature.Borate ion attacks phenol hydroxyl groups and adjacent position hydroxymethyl groups on the phenol ring of the resin, and forms the coordinate bond between boron atom in borate ion and oxygen atom in the hydroxyl groups. The complexation is a quantitative reaction. The complex is a six member ring containing two oxygens and one boron. The complexation can release hydrogen ions resulting in the decreasing pH in the resin solution.