Reaction Monitoring of Toluenediisocyanate (TDI) Polymerization on a Non-Mixable Aqueous Surface by MALDI Mass Spectrometry

Abstract

The polymerization reaction of toluene diisocyanate (TDI) and hydroxyl compounds has been widely used for the production of polyurea resins. Since the composition and molecular-weight distribution of polymer adducts greatly influence the final properties of the resuting polymer, the development of analytical tools capable of monitoring the polyaddition reactions is important to control them as well as the properties of the resuting polymer. Here we report that matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS) is useful to precisely monitor time-dependent dynamic events occurring in the polymerization reaction of TDI with water. For this purpose, the polymerization reactions were conducted in two different reaction systems, continuously supplying sufficient water and depleting water after an initial exposure of water to provide an anhydrous storage condition of prepolymer adducts. Samples prepared in a time course from the two different reaction systems were analyzed by a MALDI TOF mass spectrometer. The polymerization adducts of TDI and water were monitored and showed to consist of three structural types of polymer adduct series, including diisocyanate, monoamino, and diamino series. These MALDI mass data efficiently reflected changes in the reaction conditions of each TDI polymerization reaction, thereby providing precise information at the molecular level for time-dependent events occurring during the polymerization reaction. These events included changes between the polymer adduct series and in the molecular-weight distribution of each polymer adduct series. The results obtained in this study suggest that high-throughput MALDI MS-based dynamic monitoring of polymerization can be used to precisely control the polymerization reaction as well as to rapidly monitor the state of prepolymers in storage.