利用金屬茂及鏈轉移劑合成含立體規則性雙團聯高分子

Preparation of structurally well-defined stereoregular diblock copolymers via metallocene-mediated selective chain transfer reactions

李璟郁(Jing-Yu Lee)

指導教授 ： 蔡敬誠

國立中正大學/工學院/化學工程學系/博士(2012年)

摘要

Metallocene catalysts have attracted much attention form the both industry and academic because of their capabilities in providing architectural controls for polyolefins. In light of the important applications in the metallocene technology, this research is aiming for the development of new synthetic methods that offer the successful preparation of polypropylene-based stereoregular (including isotactic and syndiotactic) diblock copolymer.
In our reach, stereoregular diblock copolymers will be prepared by two step processes. First, end-functionalized stereoregular polypropylene was generated by conducting the selective transfer chain reaction to chain transfer reagents during the stereospecific propylene polymerization in the pressence of novel chain transfer reagents.(e.g., norbornadieneene/hydrogne (NBD), vinylsilanes/hydrogne, Triethylaluminum/ bromide),and has leads to the generation of end-functionalized stereoregular PPs end –capped with chain transfer agents. Second, post polymerization of the end-functionalized PP via using the end-functional group as the linkage proves the successful generation of stereoregular PP based aiblock copolymers, which have well defined chain structures.
Several novel diblock copolymers, including the poly(propylene)-blcok- poly(styrene) (PP-b-PS), poly(propylene)-blcok-poly(methyl methacrylate) (PP-b-PMMA), poly(propylene)-block–poly(DL-lactide) (PP-b-PLLA), poly(propylene)-blcok-poly(diphenylacrylamide) (PP-b-PDPAA) and poly(propylene)-blcok-poly(3-hexylthiophene) (PP-b-P3HT) were synthesized by the synthetic route. Our results also indicate that the stereoregular polypropylene-based diblock copolymer have uniform chemical structures and block lengths, and are suitable for use in the self-assembly studies for the construction of consistent nanostructures as revealed by TEM and SAXS analyses. Moreover, these novel synthetic routes offer the successful preparations of the structurally well-defined stereoregular polypropylene-based diblock copolymer, which are difficult to prepare by other methods.

關鍵字

鏈轉移劑 ； 金屬茂觸媒 ； 雙嵌段共聚合物

並列摘要

Metallocene catalysts have attracted much attention form the both industry and academic because of their capabilities in providing architectural controls for polyolefins. In light of the important applications in the metallocene technology, this research is aiming for the development of new synthetic methods that offer the successful preparation of polypropylene-based stereoregular (including isotactic and syndiotactic) diblock copolymer.
In our reach, stereoregular diblock copolymers will be prepared by two step processes. First, end-functionalized stereoregular polypropylene was generated by conducting the selective transfer chain reaction to chain transfer reagents during the stereospecific propylene polymerization in the pressence of novel chain transfer reagents.(e.g., norbornadieneene/hydrogne (NBD), vinylsilanes/hydrogne, Triethylaluminum/ bromide),and has leads to the generation of end-functionalized stereoregular PPs end –capped with chain transfer agents. Second, post polymerization of the end-functionalized PP via using the end-functional group as the linkage proves the successful generation of stereoregular PP based aiblock copolymers, which have well defined chain structures.
Several novel diblock copolymers, including the poly(propylene)-blcok- poly(styrene) (PP-b-PS), poly(propylene)-blcok-poly(methyl methacrylate) (PP-b-PMMA), poly(propylene)-block–poly(DL-lactide) (PP-b-PLLA), poly(propylene)-blcok-poly(diphenylacrylamide) (PP-b-PDPAA) and poly(propylene)-blcok-poly(3-hexylthiophene) (PP-b-P3HT) were synthesized by the synthetic route. Our results also indicate that the stereoregular polypropylene-based diblock copolymer have uniform chemical structures and block lengths, and are suitable for use in the self-assembly studies for the construction of consistent nanostructures as revealed by TEM and SAXS analyses. Moreover, these novel synthetic routes offer the successful preparations of the structurally well-defined stereoregular polypropylene-based diblock copolymer, which are difficult to prepare by other methods.

並列關鍵字

chain transfer agent ； Metallocene ； diblock copolymer

參考文獻

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