Attaphon Kaewvilai

Novel Recovery of Nano-Structured Ceria (CeO2) from Ce(III)-Benzoxazine Dimer Complexes via Thermal Decomposition

N,N-bis(2-hydroxybenzyl)alkylamines, benzoxazine dimers, are the major product produced from benzoxazine monomers on mono-functional phenol by the one step ring opening reaction. Due to the metal responsive property of benzoxazine dimers, in this present work, N,N-bis(5-methyl-2-hydroxybenzyl)methylamine (MMD), N,N-bis (5-ethyl-2-hydroxybenzyl)methylamine (EMD), and N,N-bis(5-methoxy-2-hydroxybenzyl) methyl amine (MeMD), are considered as novel ligands for rare earth metal ion, such as cerium(III) ion. The complex formed when the clear and colorless solutions of cerium nitrate and benzoxazine dimers were mixed, results in a brown colored solution. The metal-ligand ratios determined by the molar ratio and the Job’s methods were found to be in a ratio of 1:6. To clarify the evidence of the complex formation mechanism, the interactions among protons in benzoxazine dimers both prior to and after the formation of complexes were determined by means of 1H-NMR, 2D-NMR and a computational simulation. The single phase ceria (CeO2) was successfully prepared by thermal decomposition of the Ce(III)-benzoxazine dimer complexes at 600 °C for 2 h, was then characterized using XRD. In addition, the ceria powder investigated by TEM is spherical with an average diameter of 20 nm.

The Effect of Alkali and Ce(III) Ions on the Response Properties of Benzoxazine Supramolecules Prepared via Molecular Assembly

A series of benzoxazine monomer supramolecules with different substituted groups on their benzene ring was prepared with a Mannich reaction and characterized by FTIR, 1H-NMR and MS. The obtained products were 3,4-dihydro-3-(2’-hydroxyethylene)-6-methyl-2H-benzoxazine (BM1), 3,4-dihydro-3-(2’-hydroxyethylene)-6-ethyl-2H-benz-oxazine (BM2), and 3,4-dihydro-3-(2’-hydroxyethylene)-6-methoxy-2H-benzoxazine (BM3). The efficiency of alkali metal ion extraction from the products was determined with Pedersen’s technique, while the complexation of the Ce(III) ion was confirmed by the Job’s and the mole ratio methods. The evidence of complex formation between benzoxazine monomers and Ce(III) ions was obtained with FTIR and a computational simulation. Single phase ceria (CeO2) as observed with XRD was successfully prepared by calcinating the Ce(III)-benzoxazine monomer complexes at 600 °C for 2 h. In addition, the geometry of the ceria nanoparticles confirmed by TEM is spherical, with an average diameter of 10‑20 nm.

4,4'-Diethyl-2,2'-[(N-cyclo-hexyl-imino)-bis-(methyl-ene)]diphenol.

The title compound, C24H33NO2, exhibits an intramolecular hydrogen bond between a phenol –OH group and the N atom. In the crystal, molecules are connected by pairs of O—H⋯O hydrogen bonds.

4,4'-Dimeth-oxy-2,2'-[methyl-aza-ne-diyl-bis(methyl-ene)]diphenol.

The title compound, C17H21NO4, shows an intramolecular hydrogen bond between a phenol OH group and the N atom. In the crystal, molecules are connected by pairs of O—H⋯O hydrogen bonds into inversion dimers.

2-{[(2-Hy­droxy-3,5-dimethyl­benz­yl)(meth­yl)amino]­meth­yl}-4,6-dimethyl­phenol

In the title compound, C19H25NO2, the dihedral angle between the benzene rings is 53.15 (8)°. One of the –OH groups forms an intramolecular O—H⋯N link, generating an S(6) ring. The other –OH group forms an intermolecular O—H⋯N hydrogen bond in the crystal, generating centrosymmetric R 2 2(20) loops.