The Self-assembly Behavior Of Polymer With Nanoparticles Or Metal Ion

Macromolecular self-assembly is the inter-disciplinary of both Supramolecular Chemistry and Polymer Chemistry, is at the head of the development of chemistry as well as material science. It can also be the basement of varieties of advanced materials. It discusses mainly on how to construct the ordered nanostructure from three forces: 1 Force between polymer and polymer; 2 Force between polymer and small molecular; 3 Force between polymer and nanoparticles. Up until now, we have already achieved much success in how to construct ordered nanostructure from polymer. However, this field still needs much more attention and deeper research or discussing because of the"soft"character of polymer as well as random conformation of it. Besides, most of the ordered nanostructure reported from polymer mainly exists in the solution, there were rarely reports about the self-assembly system in the media like film or substrate. In this dissertation, I aim to broaden the scope of macromolecular self-assembly, hence we base on random polymer, and try to achieve ordered nanostructure in other media except for the solution. We summarize the results of the self-assembled nanostructure, and give the mechanism of the self-assemble process. My dissertation concludes two parts: In part one: Some oligomers containing some functional groups like thiol were synthesized with Diglycidyl ether of bisphenol (DGEBA) and trimercaptothioethylamine (TMTEA). ZnS nanoparticles were formed in situ in the oligomer matrix. While changing the factors like the molar radio of DGEBA to TMTEA, the wt% content of ZnS in the final system, the film thickness etc, we have achieved different nanostructures in the nanocomposite films. When the molar radio of thiol in TMTEA is 5% higher than the theoretical radio, and the wt% content of ZnS NPs is 5%, close packed sphere nanostructure was formed in the film. This process was from no order to order, and it is different from the traditional assembly of polymers and nanoparticles. Besides, a mechanism for this process was brought up.In part two: Styrene (St), and Glycidyl methacrylete (GMA) homopolymers were prepared by free radical initiated solution polymerization using 2,2'-azobisisobutyronitrile (AIBN) as initiator. Similarly, a series of binary copolymers were prepared with styrene (St) and other monomers like GMA, Thiiranylmethylmethacrylate (TMA), MA, and MMA. The self-assembly behavior of the homopolymers and copolymers talked above induced by solvent evaporation were discussed. The factors, like different polymer structure and concentration, different solvents, substrates, temperature, evaporation velocity and the effect of heavy metal ions etc, can all affect the final nanostructure on the substrate. A mechanism for the formation of the nanostructure was brought up.For the ordered nanostructure talked above, we also want to realize their application, so we make some Work Prospect too. For example, in chapter two, we aim to achieve the photonic crystal nanostructure in the film, so we can realize the adjustment of light; we also expect to discuss more about the polymer/ZnS nanocomposite films in the application of"high refractive index"nanocomposite films.