梳狀型帶有聚醚鏈段之高分子及其共價鍵結奈米粒子複合結構之精準合成與應用(2/3)

2009-08-012024-05-18https://scholars.lib.ntu.edu.tw/handle/123456789/699219摘要：近年在“bottom-up ＂合成製備與奈米尺寸下的操縱優勢已在材料科學與技術上有著革命性的進展。過去的研究中，本研究團隊(林江珍，陳文章，諶玉真)專研在奈米材料開發，尤其為奈米粒子的合成、高分子-無機物複合物的製備、改質與其光學及電子應用等。其中JJLin 團隊發展出高分子型多胺官能基之界面活性劑，達成層狀黏土脫層技術。脫層＂奈米矽片＂除了有吸附、觸媒、塑膠添加等廣泛應用外，亦可視為一新材料。呈現出自我排列及與有機的親合作用性等基本性質，有別於自然界中的層狀結構的插層黏土，奈米矽片的高比表面積(平均片徑100×100×1 nm3)與高電荷密度(平均每個片狀結構有18,000 離子)，預測可與高分子有著高度作用性，可設計出一系列多變化之片狀高分子的有機無機複合物。本計劃著重於奈米矽片與梳狀型rod-coil 或coil-coil 嵌段式共聚高分子以共價鍵結形成奈米矽片-高分子之新穎具有感應對答之複合物。藉由sol-gel 的製程將以帶有矽烷官能基的有機分子，用以改質奈米矽片表面之矽氧結構 (such as aminopropyl trimethoxysilane as platelet ≣Si-O-Si-CH2CH2CH2NH2 linking)或是醯鹵化合物(dibromide selective reaction) 的選擇性改質反應而帶有官能性。具有功能性的奈米矽片可進一步做精準控制的活性自由基聚合(本計畫主要以原子轉移自由基聚合方式atom transfer radical polymerization, ATRP) 。利用苯乙烯、丙烯酸酯等帶有功能性之官能基的不同單體所設計嵌段共聚高分子，同時兼具無機片狀結構的奈米矽片與溫度和酸鹼應答等多功能性的高分子鏈段，將對銀、氧化鐵及二氧化矽等奈米粒子有強的螯合性質。隨著奈米矽片-共聚高分子-奈米粒子之新穎複合物設計，將理論模擬與計算其片狀結構之奈米矽片在此新複合物的型態變化中扮演的角色，並分析此新複合物於自我排列、光學性質(UV 吸收、螢光變化)、磁性、溫度及pH 等基本性質所產生及其差異變化性。最終將這些性質利用“bottom-up ＂的製備技術與自我排列特性，將所開發之奈米矽片-共聚高分子-奈米粒子新穎複合物，衍生至感應器元件及藥物傳遞等應用，且藉由複合物所具有的磁性、pH 及溫度等應答特性作為感應元件或藥物包覆等應用。在元件應用部份，利用奈米矽片的幾何結構所具有的方向性與模板的重要特性，將奈米矽片-共聚高分子-奈米粒子複合物進行排列於高分子薄膜或無機基材表面，進一步應用濕式乾燥方式製備於導體、高介電常數與阻氣等領域。於藥物傳遞的部份，為利用此複合物因親水性的奈米矽片與有機嵌段共聚高分子的雙性特性，製備形成油水(Oil-in-Water) 微胞型態之有機/無機微結構，此複合物的特殊結構，可形成核殼包覆行為，具有應用的重要性。本計劃規劃為三年，其所製備的新穎奈米材料將由本團隊共同對型態、分析、理論模擬等基礎性質進行研究，並建立自我排列、型態與結構改變的相關基礎理論。第一年，主要著重於奈米矽片-嵌段共聚高分子與奈米粒子-嵌段共聚高分子的複合物製備。第二年，除了一系列多樣式的複合物的製備外，且藉由奈米粒子的添加，進而對其衍生性質分析。第三年，著重於應用的探討，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材料，於此領域之尖端學術研究能有突破性的發展與提升。本四人研究團隊成員分別在高分子合成、奈米材料製備與分析、型態理論計算與高分子物理等領域各有專長與經驗，所有成員將發揮所長，激盪出無限的創意，希望能提升在奈米材料的學術研究與實際應用。 <br> Abstract: Precise Synthesis and Applications of Stimuli-Responsive Microstructures Comprising of Amphiphilic Block Copolymers and Covalently Bonded Silicate Platelet/Spherical Nanoparticle Complexes (梳狀型帶有聚醚鏈段之高分子及其共價鍵結奈米粒子複合結構之精準合成與應用) Recent advances in “bottom-up” synthesis in nanotechnology and nanoscale manipulation have made a revolutionary progress in fabricating new materials and applications. In the past, several of our team members (Prof Lin, JJ, Chen, WC and Sheng, YJ) have also worked on the development of new nanomaterials particularly in the areas of inorganic nanoparticles, polymer-inorganic hybrids and their optical and electronic applications. One of the investigators (JJ Lin) has developed an exfoliating method to delaminate the layered clays into random form of nano silicate platelets (NSP). The platelet materials are different from the naturally-occurring clays with respect to the geometric structure as well as the ionic characters. The finding has promoted the clay applications from the conventional uses such as absorbents, catalysts, fillers for plastics, etc. to even broader areas. With the isolation of NSP new material in an “exfoliated” form rather than a conventional “intercalated” form, the unique properties including self-assembling behavior and hydrophilic interaction with organics have also found. Due to the presence of high surface area (average dimensions of 100×100×1 nm3) and intensive charge density (ca. 18,000 ions per platelet), the randomized NSP could be interacting well with polymers to produce a novel class of silicate platelet-polymer hybrid materials. In this proposal, we plan to synthesize a series of NSP (nanoscale silicate platelets) covalent bonding with comb-rod-coil or coil-coil or physically stimuli-responsive copolymers, in other words, to tailor and construct novel NSP-polymer hybrids. The detailed approaches involve a surface modification of the inorganic platelets via the ≡Si-O- functionalities through sol-gel process (such as aminopropyl trimethoxysilane as a platelet liking ≡Si-O-Si-CH2CH2CH2NH2) or dibromide reaction. The silicate platelets will be initiated with a precise synthesis using the well-developed free-radical living polymerization (such as ATRP). The attached diblock (comb-rod-coil and comb-coil-coil) copolymers are tailored by selecting different monomers including styrene, a variety of acrylates to construct the polymer blocks with the LCST, pH-sensitive, florescence and other stimulus-response properties. Furthermore, both portions of silicate platelets and diblock copolymers (abbreviated as NSP-Copolymer) are expected to have strong chelating properties for complexing nanoparticles such as Ag, SiO2 and magnetic Fe3O4. With the presence of the added nanoparticles, the new hybrids of NSP-Copolymer-Nanoparticules are further compounded with additional or altering functions such as the behaviors of self-assembling, UV absorption, magnetism, and the LCST/pH sensitivity. For all of these NSP-copolymers, their morphological changes in relating to their polymer structures and the role of NSP will be theoretically modeled and calculated. Ultimately we are targeting at industrial applications in the area of sensor devises and drug delivery. Their self-assembling process on the substrates of polymeric films and inorganic surfaces could affect the large-scale fabrication in aligning these hybrid units. Potential applications for solution-cast conductors, solution-cast high-k dielectrics, and permeation barriers may aid to the recent progress in these areas. For the preparation of the large scale devises, the shape of NSP (silicate platelets) may play an important role for a directional or template effect. For the drug delivery, the hybrids are considered as amphiphilic polymers with a silicate ionic as hydrophilic portion to form micelle-like Oil-in-Water (O/W) microstructures. To tailor the precise structure of NSP-copolymers is the important factor for these applications. The suitable hybrid should possess a host-guest encapsulating behavior. Both applications of sensing devise and drug encapsulation can be added with magnetic and temperature/pH properties for measuring their responsiveness. A three-year program is organized for this proposal. The prepared materials will be passed to other collaborators for the studies of morphology, analysis and theoretical calculation. The structural correlation to the fundamental theory for the morphological and self-assembling changes will be established. In the first year, we will focus on the preparation of NSP-Copolymer and their corresponding nanoparticle complexes. For the second years, besides the synthesis for more hybrids, the emphasis will be placed on the nanoparticle additions and property evaluation. In the third year, the works will concentrate on the applications. The ultimate goal is to systematically develop a family of new nanomaterials, perform a cutting-edge research and hopefully lead to a myriad of potential applications. The team consists of several experienced researchers with expertise in different fields of polymer synthesis, nanomaterial analysis, theoretical calculation for morphology and polymer physics. All team members are willing to work together to make a difference in nanotechnology research. All of us agree to work as a team to strive for excellence in both academic research and practical applications.&#63756米材&#63934黏土複合物嵌段共聚高分子&#63756米矽片&#63978子性共價鍵自我排&#63900型態環境感應感應器磁性藥物標的。nanomaterialclay hybriddiblock copolymernano silicate platelets (NSP)ionic charactercovalent bondself-assemblymorphologystimuli-responsivesensormagnetismdrug targeting.梳狀型帶有聚醚鏈段之高分子及其共價鍵結奈米粒子複合結構之精準合成與應用(2/3)