Synthesis of polybenzoxazine/clay nanocomposites by in situ thermal ring‐opening polymerization using intercalated monomer

Abstract

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.

New benzoxazines containing polyhedral oligomeric silsesquioxane from eugenol, guaiacol and vanillin

“…Significant enhancement in thermal, mechanical and physical properties of polymers can be achieved by incorporating 35 a variety of nanofillers, such as carbon nanotubes, layered silicates and polyhedral oligomeric silsesquioxanes (POSS) into the polymer backbone. This class of materials is currently facing applications in a number of areas, including optics, electronics, mechanics, energy, environment, biology, medicine, catalysis, 40 sensors etc 3,4 .…”

H-bonding supramolecular interactions driving the dispersion of kaolin into benzoxazine: A tool for the reinforcement of polybenzoxazines thermal and thermo-mechanical properties

“…Regarding clay minerals, a traditional organomodification approach is employed to promote clay dispersion in benzoxazine. This strategy relies on the exchange of the clay inter-platelets cations by a reactive and organophilic cation to enhance benzoxazine monomers diffusion within clay platelets and therefore polymer growing to reach an exfoliated state [17,18,24,25]. Recent works on carbon nanotubes/polybenzoxazine composites raise interests onto convenient composites preparations based on p-p supramolecular interactions [19,21,22], leading to outstanding reinforcement of materials.…”

“…The reinforcement strategy of benzoxazine resins generally relies on the use of polyhedral oligomeric silsesquioxanes (POSS) [10][11][12], clay minerals [13][14][15][16][17][18] or carbon nanotubes [19][20][21][22][23], which have been extensively used as polymer fillers. Regarding clay minerals, a traditional organomodification approach is employed to promote clay dispersion in benzoxazine.…”

Preparation and Properties of Hybrid Materials Originating from Polybenzoxazines and Silsesquioxanes

“…In addition, alloying or hybridizing with highly thermally stable materials, such as polyimide, multiwalled carbon nanotubes, titania, and clay, is another effective method 20–23. Recently, novel classes of organic/inorganic hybrid materials have been developed based on silsesquioxane prepared by sol‐gel methods, with a network structure 24.…”