The reversible nature of the addition reaction of 1,3-benzoxazine and thiol at ambient temperature was discovered by investigating the reaction with using p-cresolderived N-phenyl benzoxazine 1 and 1-octadecanethiol 2. The reaction was performed in several deuteriated media involving CDCl 3 and CDCl 3 + CD 3 OD, for monitoring their reaction by 1 H NMR spectrometry. CDCl 3 was a favorable solvent for the efficient progress of the reaction, and its combination with CD 3 OD allowed further acceleration of the reaction. In both cases, the reaction proceeded until conversion of 1 reached a certain ceiling value, to suggest that the reaction was reversible. This reversible nature was concretely confirmed by finding a dissociation reaction of isolated 3 into 1 and 2 in CDCl 3 . Analogously, a bisphenol A-derived bifunctional benzoxazine 4 and 1,6hexanedithiol 5 underwent the polyaddition in CDCl 3 + CD 3 OD at ambient temperature to afford the corresponding polymer 6. Successful depolymerization of 6 into small fragments was achieved by dissolving 6 in CDCl 3 .

A new class of polybenzoxazine/montmorillonite (PBz/MMT) nanocomposites has been prepared by the in situ polymerization of the typical fluid benzoxazine monomer, 3-pentyl-5-ol-3,4-dihydro-1,3-benzoxazine, with intercalated benzoxazine MMT clay. A pyridine-substituted benzoxazine was first synthesized and quaternized by 11-bromo-1-undecanol and then used for ion exchange reaction with sodium ions in MMT to obtain intercalated benzoxazine clay. Finally, this organomodified clay was dispersed in the fluid benzoxazine monomers at different loading degrees to conduct the in situ thermal ring-opening polymerization. Polymerization through the interlayer galleries of the clay led to the PBz/MMT nanocomposite formation. The morphologies of the nanocomposites were investigated by both X-ray diffraction and transmission electron microscopic techniques, which suggested the partially exfoliated/intercalated structures in the PBz matrix. Results of thermogravimetric analysis confirmed that the thermal stability and char yield of PBz nanocomposites increased with the increase of clay content.

We describe a new strategy for preparation of benzoxazine monomers based on in situ preparation of a thiol‐functionalized benzoxazine and successive chemical modification of the thiol moiety. The thiol‐functionalized benzoxazine can be prepared from its precursor bearing two benzoxazine moieties linked by disulfide bond. Reductive cleavage of the disulfide bond of the precursor with using triphenylphosphine as a reducing agent allows successful preparation of the thiol‐functionalized benzoxazine. By performing this reduction process in the presence of epoxides and acrylates, the formation of the thiol moiety and its successive reaction with those electrophiles proceed efficiently to give the corresponding benzoxazines with sulfide moieties. The benzoxazine monomers thus prepared exhibit much higher polymerization ability than those without sulfide moiety. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1448–1457

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The effect of acidic compound on the formation of active species in homolytic hydroperoxide decomposition by hindered amine light stabilizers (HALS) was studied. The hydroperoxide decomposition activity of HALS is an important to characteristics of HALS. HALS Ammonium salt, which is a fundamental compound involved in the antagonism between HALS and acidic compounds including phenolic antioxidants, was found to be a key compound for the formation of HALS nitrosonium salt, which was identifi ed as the active species of hydroperoxide decomposition. HALS Nitrosonium salt was not formed from active species for polymer stabilization, such as nitroxide, alkoxide, or hydroxylamine of HALS, but from HALS salt. A formation mechanism of HALS nitrosonium salt is proposed. Furthermore, molecular aggregates formed between HALS and acid compounds are discussed to be important for HALS properties.