α-環糊精/聚乙二醇聚輪烷及其衍生物，機械與流變性質探討

Investigation of mechanical and rheological properties for α-cyclodextrins (α-CDs) /poly (ethylene glycol) PEG polyrotaxanes and its derivatives

林柏甫(Pai-Fu Lin)

指導教授 ： 芮祥鵬

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2008年)

https://doi.org/10.6841/NTUT.2008.00092

摘要

本篇論文主要研究一種新的超分子結構”(準)聚輪烷/聚輪烷”
(polypseudorotaxanes/polyrotaxanes)，我們使用環狀超分子α-環糊精與長鏈高分子聚乙二醇合成聚輪烷，形成類似串珠的結構。α-環糊精與聚乙二醇間沒有明顯鍵結，僅有微弱氫鍵(hydrogen bonding)及凡得瓦爾力(Van der Waals force)等非共價性鍵結作用，故α-環糊精在網狀結構中形成分子間交聯點並可在長鏈中自由滑動，形成彈性材質之軟鏈與硬鏈結構。進而改變α-環糊精上的官能基，藉乙醯基化(acetylation)、羥丙基化(hydroxypropylation)得到三種不同的彈性體，以動態機械分析儀(DMA)測試其應力-應變關係(stress-strain)、蠕變及回復(creep and recovery)與收縮度(shrink)，發現當α-環糊精上的羥基被取代，氫鍵變少，彈性變好。我們更進一步將聚輪烷以交聯劑交聯，以流變儀(SR5)測試其流變性質。

關鍵字

超分子 ； 環糊精 ； 聚輪烷 ； 可滑動凝膠

並列摘要

This study focused on the synthesizing of a novel supramolecular structure “polypseudorotaxanes/polyrotaxanes.” The molecular structure was based on α-cyclodextrins (α-CDs)/poly(ethylene glycol) PEG polyrotaxanes. There was no apparent intramolecular bonding in between α-CDs and PEG, only non-covalent bonding such as hydrogen bonding and Van der Waals force were extant. Therefore, crosslink point formed between two α-CDs and it could slide along the PEG chain, thus, this soft and hard chain allows the forming of an elastic material. In addition, polyrotaxane derivatives were obtained by the polyrotaxane modification reactions such as acetylation and hydroxypropylation, and mechanical properties (stress-strain, creep and recovery & shrink) were investigated with DMA. Furthermore discovered when hydroxyl group were substituted, the elasticity of material increased due to the decreasing of hydrogen bonding. Moreover, crosslinked the polyroytaxanes with a crosslinking agent (DVS) and dynamic test was investigated with SR5.

並列關鍵字

supramolecule ； cyclodextrins ； polyrotaxanes ； the sliding gels

參考文獻

[2] Araki J., Ito K., Journal of Polymer Science, Part A: Polymer Chemistry, 2006, 44 (21), 6312-6323

[5] Pringsheim, H., Chemistry of the Saccharides., McGraw-Hill: New York, 1932, 280

[6] Pringsheim, H., A ComprehensiveSurvey of Starch Chemistry; Walton, R. P., Ed., Chemical Catalogue Co., Inc.: New York, NY, 1928; 35

[7] Freudenberg K., Rapp., W., Ber. Dtsch. Chem. Ges., 1936, 69, 2011

[8] Freudenberg K., Meyer-Delius M., Ber. Dtsch. Chem. Ges., 1938, 71, 1596