Syntheses and Self-Assembly of Stereoregular Photoluminescent Polymers and Diblock Copolymers

• Main Author: 江晟鋐
• Other Authors: 蔡敬誠
• Format: Others
• Language: zh-TW
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/handle/889522

博士 === 國立中正大學 === 化學工程研究所 === 107 === Polymers are important materials, which found broad industrial applications and various daily usages. Stereoregularity is an important issue in the polymer research as tacticity can typically offer crystallinity that elevates melting point and enhance mechanical strength of polymers for used in the valued-added engineering material applications. On the other hand, conjugated polymers have recently emerged as one of the most epic research area as conjugated polymers were expected to find potential application for used as conducting, light emitting and solar cell materials. In light of the important structural issue of stereoregularity and conjugation in polymer architecture, this study aims to synthesize novel side-chain conjugated polymers, which have a unique chemical structure of processing a conjugated side-chains stereospecifically situated along the polymer main-chain. Our experimental results demonstrated that these stereoregular side-chain conjugated polymers have a unique tacticity-dependant effect on PL properties (increase isotacticity leads to the enhancement of red shift in the wavelength of photoluminescence). In order to further elucidate the stereoregulaity effect, various stereoregular block copolymers were also synthesized. These samples were found to be able to self-assemble into ordered nanostructures, providing a structural insight the stereoregularity effect in the molecular aggregation processes. The following outline topics (research areas) which were examined in the courses of this doctoral research: I. Syntheses of conjugated monomers through Suzuki-Miyaura cross coupling reaction (for polymers with C=C bond conjugation) and through Buchwald-Hartwig amination reaction (for polymers with C=N bond conjugation). II. Syntheses of Stereoregular side-chain photoluminescent polymers via the stereospecific polymerization of conjugated monomers. The structural influence of conjugated monomers on the polymerization rate was reported. III. End-functionalized conjugated polymer was synthesized by conducting the syndiospecific polymerization of conjugated monomer in the presence of vinylsilane chain transfer agent and syndiospecific metallocence catalysts. The resulting vinylsilane end-capped conjugated polymers were used to undergo various organic transformation reactions so as to provide reactive functional group upon the chain end of stereoregular conjugated polymer. IV. Post-polymerization of the end-functionalized stereoregular conjugated prepolymers offers the successful syntheses of conjugated block containing stereoregular diblock copolymers, which were found to have the well-defined chemical structures and can be self-assembled into ordered nanomorphologies.