Methoxy-grafted kaolinite preparation by intercalation of methanol: Mechanism of its structural variability

Methoxy-grafted kaolinite is an excellent organic-inorganic compound, which serves as a precursor to prepare new organic or inorganic kaolinite hybrid materials. Direct intercalation of kaolinite with dimethyl sulfoxide (DMSO), N-methylformamide (NMF) and urea (U) was achieved. All of the above intercalated kaolinites could be grafted by methoxy groups by reacting with methanol. The pre-intercalated molecules of DMSO, NMF and U blocked the grafting action at first but facilitated it at a later stage. Here, the mechanism of the structural collapse of methoxy-grafted kaolinite was proposed. Spontaneous deintercalation of small molecules such as water, ethanol, isopropanol and others was observed. Water and methanol molecules played an important role in the grafting action and also affected the structure of methoxy-grafted kaolinite. The d(001) of methoxy-grafted kaolinite was found to be in the range of 0.99-1.11 nm in wet state but constant at 0.86 nm for dry state. 13C CP/MAS NMR analysis confirmed that inner-surface hydroxyls were replaced by methoxy groups from methanol as detected by a 13C MASNMR resonance at 51 ppm assigned to methoxy groups. 13C MASNMR spectra of intercalated kaolinites confirmed that the pre-intercalated molecules were not displaced completely even though it cannot be detected by XRD. The hygroscopicity of the pre-intercalated molecules was found to affect the structure of methoxy-grafted kaolinite.