Dual-functional linear and star POSS-containing organic–inorganic hybrid block copolymers: synthesis, self-assembly, and film property

We herein report novel POSS-containing linear and star multi-arm organic–inorganic hybrid block copolymers (BCPs) L/S -(PGMA- b -PMAPOSS) 1,2,4,6 synthesized by the core-first ATRP method. Following, crosslinking of the BCPs conducted by the reaction of the glycidyl groups in the PGMA block in the presence of trimethylamine to form the 3-dimensional network and the crosslinking cured BCPs were used for the subsequent properties characterization. Based on the chemical structures being confirmed, the self-assembly behaviors in the aqueous solution and film surface property were investigated in detail. The results showed that linear L -(PGMA- b -PMAPOSS) 2 formed typical core–shell spherical micelles where the hydrophobic PMAPOSS blocks as the core and PGMA blocks as the shell. With the increasing number of arms of the hybrid BCPs, the aggregates were tuned from spherical micelles to dendritic cylinders. Besides, with the increases in the solubility of the solvent, the aggregates tended to form the spherical morphology. The hydrophobic property of the hybrid BCPs film improved gradually from linear monobrachial BCPs to star six-arm BCPs. The thermostability of the hybrid BCPs showed similar results owing to the similar MAPOSS proportion. For the adhesive performance to the glass substrate, S -(PGMA- b -PMAPOSS) 6 possessed the best adhesive strength due to the highest density of branches. Graphical abstract The novel dual-functional linear and star POSS-containing organic-inorganic hybrid block copolymers (BCPs) L/S -(PGMA- b -PMAPOSS) 1,2,4,6 were successfully synthesized by the core-first ATRP method, then crosslinking the BCPs in the presence of trimethylamine to form the 3-dimensional network. And the self-assembly behavior in aqueous solution was studied in detail, as shown in the graphic image. In addition, the surface property, thermostability and adhesive performance were analyzed.