近年來，聚合物奈米材料之相關研究蓬勃發展，其中以團聯聚合物(Block copolymer)之研究最受到矚目，研發成果已廣泛被應用於橡膠界面工業、生物相關及光電等產業領域。因此，本研究重點在於自行合成雙團聯共聚物(Diblock copolymer)及選用市售團聯共聚物，分別嵌入層狀黏土之層隙間，形成黏土複合材料，並針對嵌入共聚物進行特性鑑定，經製備完成之團聯共聚物黏土複合材料，再進行對非離子有機污染物(NOCs)及無機重金屬吸持特性作探討。 本研究自行合成M-D及M-A雙團聯聚合物，經由NMR及GPC鑑定確定RAFT聚合法成功合成雙團聯共聚物，並能有效控制分子量分佈(Polymerdispersity index，PDI)。另外與市售雙團聯聚合物分別嵌入層狀黏土所製備之雙團聯共聚物改質黏土，經由特性分析發現，團聯共聚物已成功植入層狀矽酸鹽中，使層隙間距增加且未造成剝離，而有機碳含量也明顯增高，FTIR分析結果亦證實改質黏土表面存在羧基、胺基等官能基。根據重金屬吸附實驗得知帶有羧基之團聯共聚物改質黏土，隨著pH值上升其所帶的負電荷越多，與重金屬的親和力會越高，而在最高pH值時，有最佳的吸附效果。另外，由陰離子污染物吸附實驗可得知帶有胺基之改質黏土，在酸性環境下帶正電，並證明在低pH值時，對陰離子污染物有最佳的親和力。此外，因團聯共聚物之M鏈段具有強疏水性，可大大增加改質黏土的有機碳含量，土壤經改質後對有機污染物之分佈效果明顯較文獻結果佳。本研究製備之團聯共聚物改質黏土經研究結果顯示，確實可達成同時對非離子(BTEX)、陽離子(Pb2+、Zn2+)及陰離子(Cr2O72-)污染物兼具高吸持能力之黏土複合材料。 ;In recent years various polymer and nanomaterias have been developed. Among those, block polymers and copolymers are the most concerned for scientists due to their unique natures. Current researches have been widely applied on different areas including rubbers, biomaterials and optoelectronic and semiconductors. Therefore, this research aims at polymerization of diblock copolymer, and clay-composite materials in which polymers are intercalated into interlayer of clay. These clay-composite materials were characterized and confirmed by various analytical techniques. Such clay-composite materials are considered to greatly enhance the distribution of NOCs (Nonionic Organic Compounds), and also to increase the affinity for inorganic pollutants. The polymerization of diblock copolymer, M-D and M-A, were successfully synthesized by RAFT polymerization method and were confirmed by nuclear magnetic resonance (NMR) spectral analysis. The RAFT polymerization was capable of controling molecular weight distribution effectively which further more confirmed by Gel Permeation Chromatography (GPC) analysis. SAXS X-ray diffraction (XRD) and transmission electron microscope (TEM) were used for studying intercalated materials in the silicate. The results showed that diblock copolymers are intercalated into interlayer of clay, and maintain the structure of silicate layer. Organic carbon content by wet oxidation method indicated this successful modification. As depicted in the FT-IR spectrum, the clay composite materials displayed specific functional group of diblock copolymer. The results showed that adsorption capacity increased with increasing pH value. The dimethylaminoethyl methacrylate can be protonated (positively charged) function as anionic pollutants adsorbent. The results also provided the affinity of modified clay for Cr2O72- is increased owing to the occurrence of negative zeta potential. Thus, clay-composite material can possesses both positive and negative charges and thus can act as dual sorbents for both cationic and anionic pollutants. Sorption of BTEX by modified soil indicated that distribution coefficient of BTEX is inversely proportional to their water solubility. The diblock copolymer modifiers improved the distribution ability of nonionic organic compounds was also shown in this study.
