Surface Hybrid Self-Assembly, Mechanism, and Crystalline Behavior of a Carboxyl-Ended Hyperbranched Polyester/Platinum Complex

The self-assembly of hyperbranched polymers has attracted much attention because of their wide application. In this article, we report a new facile surface self-assembly method for a carboxyl-ended hyperbranched polyester/platinum complex (HTD-3-Pt) and obtain ordered structural microrods with a length of 10-20 μm and a width of 1 μm. The length and diameter of the self-assembled microrods could be increased to 300-600 μm and 4-5 μm, respectively, by hierarchical self-assembly. The main factors affecting the morphology of the self-assemblies, including temperature, time, solvent and solubility parameter, and relative humidity were discussed by transmission/reflection polarizing optical microscopy (TRPOM), SEM, and HRSEM. The indications for the coordination bond (-COOPt) included the appearance of a new peak at 1606 cm(-1) and its shifting to 1634 cm(-1) in the FT-IR spectra, the disappearance of the C 1s peak at about 288.6 eV, and the increase in the O 1s electron binding energy in the XPS spectra. Furthermore, an interesting crystal property of the HTD-3-Pt self-assemblies was discovered and confirmed by XRD. The study results from the surface self-assembly mechanism suggest that the coordination induction of the platinum ion play a key role in driving microphase separation between the intermolecular chains and end groups of the HTD-3-Pt to form the microrod self-assemblies. Another interesting finding was that HTD-3-Pt showed a higher catalytic activity for hydrosilylation than did a traditional homogeneous catalyst.