| Summary: | 碩士 === 國立中正大學 === 化學工程研究所 === 106 === In this research, we report that an aluminum-capped isotactic poly(1-butene) was generated as the exclusive chain transfer reaction product by using Dichloro[rac-ethylenebis(indenyl)]-zirconium(IV) to mediate the isospecific polymerization of 1-butene in the presence of triethylaluminum as the chain transfer agent. The resulting aluminum-capped iP1B can be treated with oxygen and hydrogen peroxide to provide the hydroxy-capped iP1B (iP1B-OH) as the end-functionalized prepolymer. Consequently, the resulting iP1B-OH can be converted into the tosyl-capped iP1B (iP1B-OTs) by treated it with p-toluenesulfonyl chloride. The resulting tosyl-capped iP1B(iP1B-OTs) can be used to undergo coupling reaction with the living anionic P2VP so as to give the iP1B-block-P2VP diblock with precise microstructural and block length controls. This synthetic method is able to provide various iP1B-block-P2VP diblock copolymer samples, which have various volume fraction and stereoregularity controls. Accordingly, these block copolymer samples are able to self-assemble into various nanomorphologies as evidenced by Small Angle X-ray Scattering and Transmission Electron Microscopy studies. The resulting self-assembled nanostructures have an extremely narrow length of boundary and have the potential for use as nanotemplates.
This research also focuses on the synthesis of isotactic poly(N-vinylcarbazole)(iPVK) through living cationic polymerization. In the presence of the initiating system consisting of CF3SO3H, nBu4NCl and ZnCl2, iPVK can be successfully prepared with good tacticity and molecular weight controls. We also demonstrated that the tacticity of iPVK can be precisely controlled by adding THF into the polymerization system.
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