操控高分子插層黏土之分散及其環境應答性能與奈米容器應用

2012-08-012024-05-17https://scholars.lib.ntu.edu.tw/handle/123456789/687717摘要：本計畫將利用不同親疏水性的聚醚胺或其衍生雙性高分子(例如PP-g-MA、SEBS-g-MA、SMA接枝聚醚胺)，合成一系列雙性梳狀型高分子，其本身為良好之分散劑，這可應用於各種分散應用。其中，有機改質層狀黏土，將層狀黏土表面上所夾帶的離子視為親水性的官能基，配合親油性的有機高分子組成，並藉由調整插層比例各項組成，可操控成為油溶性或水溶性之有機/無機界面活性劑。另一，實驗室開發脫層片狀黏土，在其表面利用atom transfer radicalpolymerization (ATRP)接枝高分子，設計出厚度僅1 nm的薄片型有機/無機分散劑。本計畫擬整合過去成果以三年期間詳細探討“親水/親油界面特性之黏土複合物”之更多操控及探討適合應用於環境應答性能(例如pH應答、熱與UV穩定性)與奈米容器(host/guest encapsulation)應用。第一年 親水/親油混合型插層劑及奈米有機黏土之合成特性分析與對應性質主要著重於親水/親油混合型插層劑及奈米黏土複合物製備，將探討各種高分子對層狀及片狀黏土有機化改質之合成與分析；再探討其界面特性、分散特性及相關之應用(分散其他之奈米材料，包括graphene)，並建立測試各目標奈米無機材料為之分散劑之分散性質和分散評估之系統，並選擇具優良分散劑之樣品分析黏土複合物一級結構以至於奈米容器的應用。第二年 親水/親油奈米黏土複合物之分散應用延續黏土改質研究，本計畫第二年將探討親水/親油奈米黏土複合物之分散應用，主要著重於奈米黏土複合物具有親水/親油性之界面活性劑特性及幾何型差異分散理論分散不同維度之奈米材料(例如片狀、球狀及柱狀材料)。預期此新型奈米複合物將可表達出兩種奈米材料其奈米化特性，及更進一步探討其創造出新的奈米效應與應用。第三年 親水/親油奈米黏土複合物之環境應答性與奈米容器應用，將探討奈米黏土複合物之環境應答性與奈米容器(包覆biomaterials)應用。黏土改質之設計上，在合成時選擇具有環境應答性之高分子並接枝(covalent bonding)於黏土表面，使黏土複合物具有特殊環境應答性。另外，延續第一年奈米黏土複合物，黏土種類除了層狀及片狀不同外，片徑大小不同也將表達出不同大小之奈米容器，此複合物的特殊結構，可形成核殼包覆行為，在生物領域藥物傳遞及釋放具有應用價值。並統整實際應用與基礎理論，最終目標是希望經由開發此一系列新穎奈米有機黏土材料，於此領域之尖端學術研究能有突破性的發展與提升。 <br> Abstract: Organic/inorganic nanocomposite is considered to be one of the advanced materials. In our laboratories, we have devoted to the research area of polymer modified smectite silicate clay, particularly the montmorillonite clay, and already accumulated the experience for more than ten years. However, we have worked on the interface phenomenon of polymer and layer silicate clay, control of high XRD basal spacing,their hydrophilic/hydrophobic property and the clay intercalation/exfoliation mechanism. Recently, we have published two invited review articles (J.J. Lin et al., Adv. Nanomater. 2010 Geckeler K. E., Nishide H. Eds., John Wiley & Sons, Inc. New York, pp 459–480) and (J.J. Lin et al., Mater. 2010, 3, 2588–2605). In this proposal, we further investigate the clay intercalation by using hydrophilic/hydrophobic polymers such as poly(oxyalkylene)-amine grafted PP-g-MA, SEBS-g-MA, and SMA copolymers. Further, the exfoliated silicate platelets will be prepared by the ionic exchanging exfoliation of the natural clays with polymeric amine-salts, and subsequently graft the platelets via a living polymerization technique to achieve platelets edge surface tethering with covalently bonded polymers. In this three-year project, we plan to study the hydrophilic/hydrophobic property by varying the modified polymer and will be applied for stimuli-responsive functional nano-containers. To utilize the clay-polymer hybrids, the novel nanohybrids of silicate platelets/-particle/-tubes nanomaterials or complexes will be prepared via the geometric shape in-homogeneity factor dispersing method and the corresponding functions including hydrophilic/hydrophobic dispersing properties. The content of project is described as follow: The First Year: Synthesis of Hydrophilic/Hydrophobic Nano-Clay and Studies of their Unique Properties We plan to synthesize a series of nanoscale clay through non-covalent bonding with poly(oxyalkylene)-amines grafted PP-g-MA, SEBS-g-MA and SMA polymer backbones and covalent bonding with copolymers. In other words, we plan to tailor and construct novel nano-clay/polymer hybrids. The silicates will be modified by polymers with oxyethylene/oxypropylene backbone to control the dispersion behaviors in hydrophilic and hydrophobic mediums, and also the self-aggregating nature. To realize the influence of high aspect-ratio geometric shape on dispersion ability, the combination of nano-platelets/-particle/-tubes complexes will be correlated to dispersing phenomena and fuctions. The Second Year: Hydrophilic/Hydrophobic Nano-clay for Disperse Applications We will further find the uses for the series of hydrophilic/hydrophobic nano-clay for dispersing other nanomaterials. The novel nano-platelets/-particle/-tubes nanohybrids will be prepared via the geometric shape in-homogeneity factor method and study their hydrophilic/hydrophobic property. We expect that these nano-clays can be excellent dispersants for AgNP, AuNP, FeNP, SiO2, Fe3O4, grapheme, CNT, etc. Their synergetic effect for functions will be investigated. The Third Year: Hydrophilic/Hydrophobic Nano-Clay for Stimuli-Responsive Function and Nano-Container Applications We will study the nano-clay for stimuli-responsive functions and nano-container applications for hosting other organic matters and nanoparticles with functions. The copolymer brushes containing stimuli-responsive functionalities can be precisely controlled in a selective manner toward a specific stimulus such as temperature and pH value. Furthermore, the utilization of nano-clay hybrids provides a new method for embedding biomaterials into the clay layered structure generating biomaterial/layered silicate complexes potentially useful in drug delivery or biomedical design. Other functional materials will also be considered and explored.&#63756米材&#63934黏土複合物黏土插層&#63978子性界面活性劑&#63756米&#63993子環境感應藥物標的nanomaterialclay hybridclay intercalationionic charactersurfactantnanoparticle操控高分子插層黏土之分散及其環境應答性能與奈米容器應用